N-[(het)arylethyl)] pyrazole(thio)carboxamides and their heterosubstituted analogues

ABSTRACT

The present invention relates to fungicidal N-[(het)arylethyl)] pyrazolecarboxamide or thiocarboxamide and their heterosubstituted analogues, their process of preparation and intermediate compounds for their preparation, their use as fungicides, particularly in the form of fungicidal compositions and methods for the control of phytopathogenic fungi of plants using these compounds or their compositions.

The present invention relates to fungicidal N—[(het)arylethyl)] pyrazolecarboxamide or thiocarboxamide and their heterosubstituted analogues, their process of preparation and intermediate compounds for their preparation, their use as fungicides, particularly in the form of fungicidal compositions and methods for the control of phytopathogenic fungi of plants using these compounds or their compositions.

In international patent applications WO-2004/074280, WO-2005/058833, WO-2005/085238, WO-2005/103006, WO-2006/122955, WO-2007/108483 and WO-2008/081011 certain fungicidal pyrazolecarboxamide derivatives are generically embraced in a broad disclosure of numerous compounds of the following formula:

wherein A represents a substituted 5-membered heterocyclic group that can represent various rings among which a pyrazole ring, Z can represent a hydrogen atom, an alkyl group or a cycloalkyl group and the substituted or non-substituted 2-pyridyl group is linked to the pyrazolecarboxamide moeity by means of a 2-atoms linker. However, there is no explicite disclosure or suggestion to select in these documents of any such derivative wherein A represent a 1-alkyl-3-(difluoro or dichloro)methyl-5-(chloro or fluoro)-4-pyrazolyl group.

In international patent applications WO-2006/008193, WO-2006/008194, WO-2006/108791, WO-2006/117358, WO-2007/006739, WO-2008/151828, WO-2009/003672, WO-2010/084078 and WO-2011/003683 certain fungicidal pyrazolecarboxamide derivatives are generically embraced in a broad disclosure of numerous compounds of the following formula:

wherein A represents a substituted 5-membered heterocyclic group that can represent various rings among which a pyrazole ring, Z can represent a hydrogen atom, an alkyl group, an alkoxy group or a cycloalkyl group and Het can represent various substituted or non-substituted (fused)-5- and 6-membered heterocycles which are linked to the pyrazolecarboxamide moeity by means of a 2-atoms linker. However, there is no explicite disclosure or suggestion to select in these documents of any such derivative wherein A represent a 1-alkyl-3-(difluoro or dichloro)methyl-5-(chloro or fluoro)-4-pyrazolyl group.

In international patent applications WO-2006/016708, WO-2007/060164, WO-2007/060166, WO-2007/134799, WO-2007/0141009, WO-2007/144174, WO-2008/148570, WO-2010/063700, JP-2007/210924 and JP-2008/115084 certain fungicidal pyrazolecarboxamide derivatives are generically embraced in a broad disclosure of numerous compounds of the following formula:

wherein A represents a substituted 5-membered heterocyclic group that can represent various rings among which a pyrazole ring, Z can represent a hydrogen atom, an alkyl group, an alkoxy group or a cycloalkyl group and Ar can represent a substituted or non-substituted phenyl or naphthyl group which is linked to the pyrazolecarboxamide moeity by means of a 2-atoms linker. However, there is no explicite disclosure or suggestion to select in these documents of any such derivative wherein A represent a 1-alkyl-3-(difluoro or dichloro)methyl-5-(chloro or fluoro)-4-pyrazolyl group.

It is always of high-interest in the field of agrochemicals to use pesticidal compounds more active than the compounds already known by the man ordinary skilled in the art whereby reduced amounts of compound can be used whilst retaining equivalent efficacy.

Furthermore, the provision of new pesticidal compounds with a higher efficacy strongly reduces the risk of appearance of resistant strains in the fungi to be treated.

We have now found a new family of compounds which show enhanced fungicidal activity over the general known family of such compounds.

Accordingly, the present invention provides a N—[(het)arylethyl)] pyrazolecarboxamide or thiocarboxamide derivative of formula (I)

wherein

-   -   X¹ and X² which can be the same or different, represent a         halogen atom;     -   Y represents a C₁-C₄-alkyl;     -   T represents O or S;     -   W represents CZ⁴Z⁵; O; S; SO; SO₂; NZ⁶; SiZ⁷Z⁸; or —C(═U)—;     -   B represents a phenyl ring that can be substituted by up to 5         groups X which can be the same or different; a naphthyl ring         that can be substituted by up to 7 groups X which can be the         same or different; or a saturated, partially saturated or         unsaturated, monocyclic or fused bicyclic 4-, 5-, 6-, 7-, 8-,         9-, 10-membered ring comprising from 1 up to 4 heteroaroms         selected in the list consisting of N, O, S, that can be         substituted by up to 6 groups X which can be the same or         different;     -   X represents a halogen atom; nitro; cyano; isonitrile; hydroxy;         amino; sulfanyl; pentafluoro-λ⁶-sulfanyl; formyl; formyloxy;         formylamino; substituted or non-substituted         (hydroxyimino)-C₁-C₈-alkyl; substituted or non-substituted         (C₁-C₈-alkoxyimino)-C₁-C₈-alkyl; substituted or non-substituted         (C₂-C₈-alkenyloxyimino)-C₁-C₈-alkyl; substituted or         non-substituted (C₂-C₈-alkynyloxyimino)-C₁-C₈-alkyl; substituted         or non-substituted (benzyloxyimino)-C₁-C₈-alkyl; carboxy;         carbamoyl; N-hydroxycarbamoyl; carbamate; substituted or         non-substituted C₁-C₈-alkyl; C₁-C₈-halogenoalkyl having 1 to 5         halogen atoms; substituted or non-substituted C₂-C₈-alkenyl;         C₂-C₈-halogenoalkenyl having 1 to 5 halogen atoms; substituted         or non-substituted C₂-C₈-alkynyl; C₂-C₈-halogenoalkynyl having 1         to 5 halogen atoms; substituted or non-substituted C₁-C₈-alkoxy;         C₁-C₈-halogenoalkoxy having 1 to 5 halogen atoms; substituted or         non-substituted C₁-C₈-alkylsulfanyl; C₁-C₈-halogenoalkylsulfanyl         having 1 to 5 halogen atoms; substituted or non-substituted         C₁-C₈-alkylsulfinyl; C₁-C₈-halogenoalkylsulfinyl having 1 to 5         halogen atoms; substituted or non-substituted         C₁-C₈-alkylsulfonyl; C₁-C₈-halogenoalkylsulfonyl having 1 to 5         halogen atoms; substituted or non-substituted C₁-C₈-alkylamino;         substituted or non-substituted di-C₁-C₈-alkylamino; substituted         or non-substituted C₂-C₈-alkenyloxy; C₂-C₈-halogenoalkenyloxy         having 1 to 5 halogen atoms; substituted or non-substituted         C₃-C₈-alkynyloxy; C₂-C₈-halogenoalkynyloxy having 1 to 5 halogen         atoms; substituted or non-substituted C₃-C₇-cycloalkyl;         C₃-C₇-halogenocycloalkyl having 1 to 5 halogen atoms;         substituted or non-substituted (C₃-C₇-cycloalkyl)-C₁-C₈-alkyl;         substituted or non-substituted (C₃-C₇-cycloalkyl)-C₂-C₈-alkenyl;         substituted or non-substituted (C₃-C₇-cycloalkyl)-C₂-C₈-alkynyl;         substituted or non-substituted tri(C₁-C₈-alkyl)silyl;         substituted or non-substituted         tri(C₁-C₈-alkyl)silyl-C₁-C₈-alkyl; substituted or         non-substituted C₁-C₈-alkylcarbonyl; C₁-C₈-halogenoalkylcarbonyl         having 1 to 5 halogen atoms; substituted or non-substituted         C₁-C₈-alkylcarbonyloxy; C₁-C₈-halogenoalkylcarbonyloxy having 1         to 5 halogen atoms; substituted or non-substituted         C₁-C₈-alkylcarbonylamino; C₁-C₈-halogenoalkyl-carbonylamino         having 1 to 5 halogen atoms; substituted or non-substituted         C₁-C₈-alkoxycarbonyl; C₁-C₈-halogenoalkoxycarbonyl having 1 to 5         halogen atoms; substituted or non-substituted         C₁-C₈-alkyloxycarbonyloxy; C₁-C₈-halogenoalkoxycarbonyloxy         having 1 to 5 halogen atoms; substituted or non-substituted         C₁-C₈-alkylcarbamoyl; substituted or non-substituted         di-C₁-C₈-alkylcarbamoyl; substituted or non-substituted         C₁-C₈-alkylaminocarbonyloxy; substituted or non-substituted         di-C₁-C₈-alkylaminocarbonyloxy; substituted or non-substituted         N—(C₁-C₈-alkyl)hydroxy carbamoyl; substituted or non-substituted         C₁-C₈-alkoxycarbamoyl; substituted or non-substituted         N—(C₁-C₈-alkyl)-C₁-C₈-alkoxycarbamoyl; aryl that can be         substituted by up to 6 groups Q which can be the same or         different; C₁-C₈-arylalkyl that can be substituted by up to 6         groups Q which can be the same or different; C₂-C₈-arylalkenyl         that can be substituted by up to 6 groups Q which can be the         same or different; C₂-C₈-arylalkynyl that can be substituted by         up to 6 groups Q which can be the same or different; aryloxy         that can be substituted by up to 6 groups Q which can be the         same or different; arylsulfanyl that can be substituted by up to         6 groups Q which can be the same or different; arylamino that         can be substituted by up to 6 groups Q which can be the same or         different; C₁-C₈-arylalkyloxy that can be substituted by up to 6         groups Q which can be the same or different;         C₁-C₈-arylalkylsulfanyl that can be substituted by up to 6         groups Q which can be the same or different; or         C₁-C₈-arylalkylamino that can be substituted by up to 6 groups Q         which can be the same or different; or     -   two substituents X together with the consecutive carbon atoms to         which they are linked can form a 5- or 6-membered, saturated         carbocycle or saturated heterocycle, which can be substituted by         up to four groups Q which can be the same or different;     -   Z¹ represents a hydrogen atom; a formyl group; a substituted or         non-substituted C₁-C₈-alkyl; substituted or non substituted         C₁-C₈-alkoxy; non-substituted C₃-C₇-cycloalkyl or a         C₃-C₇-cycloalkyl substituted by up to 10 atoms or groups that         can be the same or different and that can be selected in the         list consisting of halogen atoms, cyano, C₁-C₈-alkyl,         C₁-C₈-halogenoalkyl comprising up to 9 halogen atoms that can be         the same or different, C₁-C₈-alkoxy, C₁-C₈-halogenoalkoxy         comprising up to 9 halogen atoms that can be the same or         different, C₁-C₈-alkoxycarbonyl, C₁-C₈-halogenoalkoxycarbonyl         comprising up to 9 halogen atoms that can be the same or         different, C₁-C₈-alkylaminocarbonyl or         di-C₁-C₈-alkylaminocarbonyl;     -   Z², Z³, Z⁴ and Z⁵ independently represent a hydrogen atom; a         halogen atom; cyano; substituted or non-substituted C₁-C₈-alkyl;         C₁-C₈-halogenoalkyl having 1 to 5 halogen atoms; substituted or         non-substituted C₁-C₈-alkoxy; substituted or non-substituted         C₁-C₈-alkylsulfanyl; or substituted or non-substituted         C₁-C₈-alkoxycarbonyl; or     -   two substituents Z^(i) and Z^(i+1), i being an integer between 2         and 4, together with the consecutive carbon atoms to which they         are linked can form a 3-, 4-, 5-, 6- or 7-membered saturated         carbocycle that can be substituted by up to four groups that can         be the same or different and that can be selected in the list         consisting of halogen atoms, C₁-C₈-alkyl or C₁-C₂-halogenoalkyl         comprising up to 5 halogen atoms that can be the same or         different;     -   Z⁶ represents a hydrogen atom; a substituted or non-substituted         C₁-C₈-alkyl; a C₁-C₈-halogenoalkyl comprising up to 9 halogen         atoms that can be the same or different; a substituted or         non-substituted C₂-C₈-alkenyl; a C₂-C₈-halogenoalkenyl         comprising up to 9 halogen atoms that can be the same or         different; a substituted or non-substituted C₃-C₈-alkynyl; a         C₃-C₈-halogenoalkynyl comprising up to 9 halogen atoms that can         be the same or different; a substituted or non-substituted         C₃-C₇-cycloalkyl; a C₃-C₇-halogeno-cycloalkyl comprising up to 9         halogen atoms that can be the same or different; a substituted         or non-substituted C₃-C₇-cycloalkyl-C₁-C₈-alkyl; formyl; a         substituted or non-substituted C₁-C₈-alkylcarbonyl;         C₁-C₈-halogenoalkylcarbonyl comprising up to 9 halogen atoms         that can be the same or different; a substituted or         non-substituted C₁-C₈-alkoxycarbonyl;         C₁-C₈-halogenoalkoxycarbonyl comprising up to 9 halogen atoms         that can be the same or different; a substituted or         non-substituted C₁-C₈-alkylsulphonyl;         C₁-C₈-halogenoalkylsulphonyl comprising up to 9 halogen atoms         that can be the same or different; phenylmethylene that can be         substituted by up to 7 groups Q which can be the same or         different; or phenylsulphonyl that can be substituted by up to 5         groups Q which can be the same or different;     -   Z⁷ and Z⁸ independently represent a substituted or         non-substituted C₁-C₈-alkyl;     -   U represents 0; S; N—OR^(a) or N—CN;     -   R^(a) represents a hydrogen atom; a substituted or         non-substituted C₁-C₄-alkyl; or a C₁-C₄-halogenoalkyl comprising         up to 7 halogen atoms that can be the same or different;     -   Q independently represents a halogen atom; cyano; nitro;         substituted or non-substituted C₁-C₈-alkyl; C₁-C₈-halogenoalkyl         having 1 to 9 halogen atoms that can be the same or different;         substituted or non-substituted C₁-C₈-alkoxy;         C₁-C₈-halogenoalkoxy having 1 to 9 halogen atoms that can be the         same or different; substituted or non-substituted         C₁-C₈-alkylsulfanyl; C₁-C₈-halogenoalkylsulfanyl having 1 to 9         halogen atoms that can be the same or different; substituted or         non-substituted tri(C₁-C₈)alkylsilyl; substituted or         non-substituted tri(C₁-C₈)alkylsilyl-C₁-C₈-alkyl; substituted or         non-substituted (C₁-C₈-alkoxyimino)-C₁-C₈-alkyl; or substituted         or non-substituted (benzyloxyimino)-C₁-C₈-alkyl;     -   as well as its salts, N-oxydes, metallic complexes, metalloidic         complexes and optically active isomers.

For the compounds according to the invention, the following generic terms are generally used with the following meanings:

-   -   halogen means fluorine, bromine, chlorine or iodine.     -   carboxy means —C(═O)OH;     -   carbonyl means —C(═O)—;     -   carbamoyl means —C(═O)NH₂;     -   N-hydroxycarbamoyl means —C(═O)NHOH;     -   SO represents a sulfoxyde group;     -   SO₂ represents a sulfone group;     -   an alkyl group, an alkenyl group and an alkynyl group as well as         moieties containing these terms, can be linear or branched;     -   the aryl moeity contained in an aryl group, an arylalkyl group,         an arylalkenyl group and an arylalkynyl group as well as         moieties containing these terms, can be a phenyl group that can         be substituted by up to 5 groups Q which can be the same or         different, a naphthyl group that can be substituted by up to 7         groups Q which can be the same or different or a pyridyl group         that can be substituted by up to 4 groups Q which can be the         same or different;     -   heteroatom means sulphur, nitrogen or oxygen.     -   in the case of an amino group or the amino moiety of any other         amino-comprising group, substituted by two substituent that can         be the same or different, the two substituent together with the         nitrogen atom to which they are linked can form a heterocyclyl         group, preferably a 5- to 7-membered heterocyclyl group, that         can be substituted or that can include other hetero atoms, for         example a morpholino group or piperidinyl group.     -   unless indicated otherwise, a group or a substituent that is         substituted according to the invention can be substituted by one         or more of the following groups or atoms: a halogen atom, a         nitro group, a hydroxy group, a cyano group, an amino group, a         sulfanyl group, a pentafluoro-λ⁶-sulfanyl group, a formyl group,         a formyloxy group, a formylamino group, a carbamoyl group, a         N-hydroxycarbamoyl group, a carbamate group, a         (hydroxyimino)-C₁-C₆-alkyl group, a C₁-C₈-alkyl, a         tri(C₁-C₈-alkyl)silyl-C₁-C₈-alkyl, C₁-C₈-cycloalkyl,         tri(C₁-C₈-alkyl)silyl-C₁-C₈-cycloalkyl, a C₁-C₈-halogenoalkyl         having 1 to 5 halogen atoms, a C₁-C₈-halogenocycloalkyl having 1         to 5 halogen atoms, a C₂-C₈-alkenyl, a C₂-C₈-alkynyl, a         C₂-C₈-alkenyloxy, a C₂-C₈-alkynyloxy, a C₁-C₈-alkylamino, a         di-C₁-C₈-alkylamino, a C₁-C₈-alkoxy, a C₁-C₈-halogenoalkoxy         having 1 to 5 halogen atoms, a C₁-C₈-alkylsulfanyl, a         C₁-C₈-halogenoalkylsulfanyl having 1 to 5 halogen atoms, a         C₂-C₈-alkenyloxy, a C₂-C₈-halogenoalkenyloxy having 1 to 5         halogen atoms, a C₃-C₈-alkynyloxy, a C₃-C₈-halogenoalkynyloxy         having 1 to 5 halogen atoms, a C₁-C₈-alkylcarbonyl, a         C₁-C₈-halogenoalkylcarbonyl having 1 to 5 halogen atoms, a         C₁-C₈-alkylcarbamoyl, a di-C₁-C₈-alkylcarbamoyl, a         N—C₁-C₈-alkyloxycarbamoyl, a C₁-C₈-alkoxycarbamoyl, a         N—C₁-C₈-alkyl-C₁-C₈-alkoxycarbamoyl, a C₁-C₈-alkoxycarbonyl, a         C₁-C₈-halogenoalkoxycarbonyl having 1 to 5 halogen atoms, a         C₁-C₈-alkylcarbonyloxy, a C₁-C₈-halogenoalkylcarbonyloxy having         1 to 5 halogen atoms, a C₁-C₈-alkylcarbonylamino, a         C₁-C₈-halogenoalkylcarbonylamino having 1 to 5 halogen atoms, a         C₁-C₈-alkylaminocarbonyloxy, a di-C₁-C₈-alkylaminocarbonyloxy, a         C₁-C₈-alkyloxycarbonyloxy, a C₁-C₈-alkylsulfinyl, a         C₁-C₈-halogenoalkylsulfinyl having 1 to 5 halogen atoms, a         C₁-C₈-alkylsulfonyl, a C₁-C₈-halogenoalkylsulfonyl having 1 to 5         halogen atoms, a C₁-C₈-alkylaminosulfamoyl, a         di-C₁-C₈-alkylaminosulfamoyl, a (C₁-C₆-alkoxyimino)-C₁-C₆-alkyl,         a (C₁-C₆-alkenyloxyimino)-C₁-C₆-alkyl, a         (C₁-C₆-alkynyloxyimino)-C₁-C₆-alkyl, a 2-oxopyrrolidin-1-yl,         (benzyloxyimino)-C₁-C₆-alkyl, C₁-C₈-alkoxyalkyl,         C₁-C₈-halogenoalkoxyalkyl having 1 to 5 halogen atoms,         benzyloxy, benzylsulfanyl, benzylamino, phenoxy, phenylsulfanyl,         or phenylamino.

Any of the compounds of the present invention can exist in one or more optical or chiral isomer forms depending on the number of asymmetric centres in the compound. The invention thus relates equally to all the optical isomers and to their racemic or scalemic mixtures (the term “scalemic” denotes a mixture of enantiomers in different proportions) and to the mixtures of all the possible stereoisomers, in all proportions. The diastereoisomers and/or the optical isomers can be separated according to the methods which are known per se by the man ordinary skilled in the art.

Any of the compounds of the present invention can also exist in one or more geometric isomer forms depending on the number of double bonds in the compound. The invention thus relates equally to all geometric isomers and to all possible mixtures, in all proportions. The geometric isomers can be separated according to general methods, which are known per se by the man ordinary skilled in the art.

Any of the compounds of the present invention can also exist in one or more geometric isomer forms depending on the relative position (syn/anti or cis/trans) of the substituents of ring B. The invention thus relates equally to all syn/anti (or cis/trans) isomers and to all possible syn/anti (or cis/trans) mixtures, in all proportions. The syn/anti (or cis/trans) isomers can be separated according to general methods, which are known per se by the man ordinary skilled in the art.

Any of the compounds of formula (I) wherein X represents a hydroxy, a sulfanyl group or an amino group may be found in its tautomeric form resulting from the shift of the proton of said hydroxy, sulfanyl or amino group. Such tautomeric forms of such compounds are also part of the present invention. More generally speaking, all tautomeric forms of compounds of formula (I) wherein X represents a hydroxy, a sulfanyl group or an amino group, as well as the tautomeric forms of the compounds which can optionally be used as intermediates in the preparation processes and which will be defined in the description of these processes, are also part of the present invention.

Preferred compounds according to the invention are compounds of formula (I) wherein X¹ and X² independently represent a chlorine or a fluorine atom. More preferred compounds according to the invention are compounds of formula (I) wherein X¹ and X² represent a fluorine atom.

Other preferred compounds according to the invention are compounds of formula (I) wherein Y represents methyl.

Other preferred compounds according to the invention are compounds of formula (I) wherein T represents O.

Other preferred compounds according to the invention are compounds of formula (I) wherein B represents a substituted or non-substituted phenyl ring; a substituted or non-substituted naphthyl ring; a substituted or non-substituted pyridyl ring; a substituted or non-substituted thienyl ring; or a substituted or non-substituted benzothienyl ring; more preferred compounds according to the invention are compounds of formula (I) wherein B represents a substituted or non-substituted phenyl ring; other more preferred compounds according to the invention are compounds of formula (I) wherein B represents a substituted or non-substituted 2-pyridyl ring;

Other preferred compounds according to the invention are compounds of formula (I) wherein X independently represents a halogen atom; substituted or non-substituted C₁-C₈-alkyl; C₁-C₈-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different; substituted or non-substituted tri(C₁-C₈-alkyl)silyl; substituted or non-substituted C₁-C₈-alkoxy or C₁-C₈-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different; substituted or non-substituted C₁-C₈-alkylsulfanyl or C₁-C₈-halogenoalkylsulfanyl comprising up to 9 halogen atoms that can be the same or different; or wherein two consecutive substituents X together with the phenyl ring form a substituted or non-substituted cyclopentyl or cyclohexyl ring.

Even more preferred compounds according to the invention are compounds of formula (I) wherein X independently represents fluorine, chlorine, bromine, iodine, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secbutyl, terbutyl, cyclopropyl, cyclopentyl, cyclohexyl, trimethylsilyl, methoxy, ethoxy, methylsulfanyl, ethylsulfanyl, trifluoromethyl, trichloromethyl, difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, trifluoroethoxy, difluoromethysulfanyl, trifluoromethylsulfanyl and difluorochloro-methylsulfanyl;

Other preferred compounds according to the invention are compounds of formula (I) wherein Z¹ represents a hydrogen atom; a non-substituted C₃-C₇ cycloalkyl; or a C₃-C₇ cycloalkyl substituted by up to 10 groups or atoms that can be the same or different and that can be selected in the list consisting of halogen atoms, C₁-C₈-alkyl, C₁-C₈-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different, C₁-C₈-alkoxy or C₁-C₈-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different; more preferably Z¹ represents a non-substituted C₃-C₇-cycloalkyl; even more preferably Z¹ represents cyclopropyl;

Other preferred compounds according to the invention are compounds of formula (I) wherein Z², Z³, Z⁴ and Z⁵ independently represent a hydrogen atom, a fluorine atom, a substituted or non-substituted C₁-C₈-alkyl or a substituted or non-substituted C₁-C₈-alkoxy;

Other preferred compounds according to the invention are compounds of formula (I) wherein two substituent Z^(i) and Z^(i+1), i being an integer between 2 and 4, together with the consecutive carbon atoms to which they are linked can form an optionally mono or polysubstituted 3-, 4-, 5-, 6- or 7-membered saturated carbocycle; more preferably an optionally mono or polysubstituted cyclopropyl, cyclopentyl, cyclohexyl or a cycloheptyl ring; even more preferably a cyclopropyl, a cyclopentyl or a cyclohexyl ring;

Other more preferred compounds according to the invention are compounds of formula (I) wherein Z³ and Z⁴ together with the consecutive carbon atoms to which they are linked can form an cyclopentyl group that can be substituted by up to three groups that can be the same or different and that can be selected in the list consisting of fluorine, chlorine, methyl, ethyl, propyl, isopropyl, isobutyl, secbutyl, terbutyl, trifluoromethyl or difluoromethyl;

Other more preferred compounds according to the invention are compounds of formula (I) wherein Z³ and Z⁴ together with the consecutive carbon atoms to which they are linked can form an cyclohexyl group that can be substituted by up to four groups that can be the same or different and that can be selected in the list consisting of fluorine, chlorine, methyl, ethyl, propyl, isopropyl, isobutyl, secbutyl, terbutyl, trifluoromethyl or difluoromethyl;

Other more preferred compounds according to the invention are compounds of formula (I) wherein Z³ and Z⁴ together with the consecutive carbon atoms to which they are linked can form an cycloheptyl group that can be substituted by up to four groups that can be the same or different and that can be selected in the list consisting of fluorine, chlorine, methyl, ethyl, propyl, isopropyl, isobutyl, secbutyl, terbutyl, trifluoromethyl or difluoromethyl;

Other preferred compounds according to the invention are compounds of formula (I) wherein Z⁶ represents a substituted or non-substituted C₁-C₈-alkyl;

Other preferred compounds according to the invention are compounds of formula (I) wherein Z⁷ and Z⁸ independently represent a non-substituted C₁-C₈-alkyl. More preferably, Z⁷ and Z⁸ independently represent a non-substituted C₁-C₃-alkyl. Even more preferably, Z⁷ and Z⁸ represent methyl.

Other preferred compounds according to the invention are compounds of formula (I) wherein U represents O.

Other preferred compounds according to the invention are compounds of formula (I) wherein U represents N—O—(C₁-C₄-alkyl).

The above mentioned preferences with regard to the substituents of the compounds according to the invention can be combined in various manners. These combinations of preferred features thus provide sub-classes of compounds according to the invention. Examples of such sub-classes of preferred compounds according to the invention can be combined:

-   -   preferred features of X¹ with preferred features of X², Y, T, B,         Z¹, Z², Z³, Z⁴, Z⁵, Z⁶, Z⁷, Z⁸, X and U;     -   preferred features of X² with preferred features of X¹, Y, T, B,         Z¹, Z², Z³, Z⁴, Z⁵, Z⁶, Z⁷, Z⁸, X and U;     -   preferred features of Y with preferred features of X¹, X², T, B,         Z¹, Z², Z³, Z⁴, Z⁵, Z⁶, Z⁷, Z⁸, X and U;     -   preferred features of T with preferred features of X¹, X², Y, B,         Z¹, Z², Z³, Z⁴, Z⁵, Z⁶, Z⁷, Z⁸, X and U;     -   preferred features of B with preferred features of X¹, X², Y, T,         Z¹, Z², Z³, Z⁴, Z⁵, Z⁶, Z⁷, Z⁸, X and U;     -   preferred features of Z¹ with preferred features of X¹, X², Y,         T, B, Z², Z³, Z⁴, Z⁵, Z⁶, Z⁷, Z⁸, X and U;     -   preferred features of Z² with preferred features of X¹, X², Y,         T, B, Z¹, Z³, Z⁴, Z⁵, Z⁶, Z⁷, Z⁸, X and U;     -   preferred features of Z³ with preferred features of X¹, X², Y,         T, B, Z¹, Z², Z⁴, Z⁵, Z⁶, Z⁷, Z⁸, X and U;     -   preferred features of Z⁴ with preferred features of X¹, X², Y,         T, B, Z¹, Z², Z³, Z⁵, Z⁶, Z⁷, Z⁸, X and U;     -   preferred features of Z⁵ with preferred features of X¹, X², Y,         T, B, Z¹, Z², Z³, Z⁴, Z⁶, Z⁷, Z⁸, X and U;     -   preferred features of Z⁶ with preferred features of X¹, X², Y,         T, B, Z¹, Z², Z³, Z⁴, Z⁵, Z⁷, Z⁸, X and U;     -   preferred features of Z⁷ with preferred features of X¹, X², Y,         T, B, Z¹, Z², Z³, Z⁴, Z⁵, Z⁶, Z⁸, X and U;     -   preferred features of Z⁸ with preferred features of X¹, X², Y,         T, B, Z¹, Z², Z³, Z⁴, Z⁵, Z⁶, Z⁷, X and U;     -   preferred features of X with preferred features of X¹, X², Y, T,         B, Z¹, Z², Z³, Z⁴, Z⁵, Z⁶, Z⁷, Z⁸ and U;     -   preferred features of U with preferred features of X¹, X², Y, T,         B, Z¹, Z², Z³, Z⁴, Z⁵, Z⁶, Z⁷, Z⁸ and x;

In these combinations of preferred features of the substituents of the compounds according to the invention, the said preferred features can also be selected among the more preferred features of each of X¹, X², Y, T, B, Z¹, Z², Z³, Z⁴, Z⁵, Z⁶, Z⁷, Z⁸, X and U, so as to form most preferred subclasses of compounds according to the invention.

The present invention also relates to a process for the preparation of the compound of formula (I).

Thus, according to a further aspect of the present invention there is provided a process P1 for the preparation of a compound of formula (I) as herein-defined and wherein T represents O and that comprises reacting a N-substituted amine derivative of formula (II) or one of its salts:

wherein Z¹, Z², Z³, W and B are as herein-defined; with a carboxylic acid derivative of formula (III):

wherein X¹, X² and Y are as herein-defined and L¹ represents a leaving group selected in the list consisting of a halogen atom, a hydroxyl group, —OR^(b), —OC(═O)R^(b), R^(b) being a substituted or non-substituted C₁-C₆-alkyl, a substituted or non-substituted C₁-C₆-haloalkyl, a benzyl, a 4-methoxybenzyl or a pentafluorophenyl group; in the presence of a catalyst and in the presence of a condensing agent in case L¹ represents a hydroxyl group, and in the presence of an acid binder in case L¹ represents a halogen atom.

N-substituted amine derivatives of formula (II) are known or can be prepared by known processes such as reductive amination of aldehyde or ketone (Bioorganics and Medicinal Chemistry Letters (2006), 2014), or reduction of imines (Tetrahedron (2005), 11689), or nucleophilic substitution of halogen, mesylate or tosylate (Journal of Medicinal Chemistry (2002), 3887).

Carboxylic acid derivatives of formula (III) can be prepared according to process P2.

In case L¹ represents a hydroxy group, the process according to the present invention is conducted in the presence of condensing agent. Suitable condensing agent may be selected in the non limited list to consisting of acid halide former, such as phosgene, phosphorous tribromide, phosphorous trichloride, phosphorous pentachloride, phosphorous trichloride oxide or thionyl chloride; anhydride former, such as ethyl chloroformate, methyl chloroformate, isopropyl chloroformate, isobutyl chloroformate or methanesulfonyl chloride; carbodiimides, such as N,N′-dicyclohexylcarbodiimide (DCC) or other customary condensing agents, such as phosphorous pentoxide, polyphosphoric acid, N,N′-carbonyl-diimidazole, 2-ethoxy-N-ethoxycarbonyl-1,2-dihydroquinoline (EEDQ), triphenylphosphine/tetrachloro-methane, 4-(4,6-dimethoxy[1.3.5]-triazin-2-yl)-4-methylmorpholinium chloride hydrate or bromo-tripyrrolidino-phosphonium-hexafluorophosphate.

The process according to the present invention is conducted in the presence of a catalyst. Suitable catalyst may be selected in the list consisting of 4-dimethyl-aminopyridine, 1-hydroxy-benzotriazole or dimethylformamide.

In case L¹ represents a halogen atom, the process according to the present invention is conducted in the presence of an acid binder. Suitable acid binders for carrying out process P1 according to the invention are in each case all inorganic and organic bases that are customary for such reactions. Preference is given to using alkaline earth metal, alkali metal hydride, alkali metal hydroxides or alkali metal alkoxides, such as sodium hydroxide, sodium hydride, calcium hydroxide, potassium hydroxide, potassium tert-butoxide or other ammonium hydroxide, alkali metal carbonates, such as cesium carbonate, sodium carbonate, potassium carbonate, potassium bicarbonate, sodium bicarbonate, alkali metal or alkaline earth metal acetates, such as sodium acetate, potassium acetate, calcium acetateand also tertiary amines, such as trimethylamine, triethylamine, diisopropylethylamine, tributylamine, N,N-dimethylaniline, pyridine, N-methylpiperidine, N,N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclo-nonene (DBN) or diazabicycloundecene (DBU).

It is also possible to work in the absence of an additional condensing agent or to employ an excess of the amine component, so that it simultaneously acts as acid binder agent.

According to a further aspect according to the invention, there is provided a process P2 for the preparation of carboxylic acid derivatives of formula (III) wherein T represents O and illustrated according to the following reaction scheme:

wherein X² is as herein-defined; 5-chloro-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carbaldehyde is known from WO-2004/014138 (reference example 35). Step 1 of process P2 is performed in the presence of an oxidant, and if appropriate in the presence of a solvent. Steps 2 and 5 of process P2 are performed in the presence of acid halide, and if appropriate in the presence of a solvent. Step 3 of process P2 is performed in the presence of a fluorinating agent, and if appropriate in the presence of a solvent. Step 4 of process P2 is performed in the presence of an acid or a base and if appropriate in the presence of a solvent

Suitable oxidants for carrying out step 1 of process P2 according to the invention are in each case all inorganic and organic oxidant which are customary for such reactions. Preference is given to using benzyltriethylammonium permanganate, bromine, chlorine, m-chloroperbenzoic acid, chromic acid, chromium (VI) oxide, hydrogen peroxide, hydrogen peroxide-boron trifluoride, hydrogen peroxide-urea, 2-hydroxyperoxyhexafluoro-2-propanol; Iodine, oxygen-platinum catalyst, perbenzoic acid, peroxyacetyl nitrate, potassium permanganate, potassium ruthenate, pyridinium dichromate, ruthenium (VIII) oxide, silver (I) oxide, silver (II) oxide, silver nitrite, sodium chlorite, sodium hypochlorite, or 2,2,6,6-tetramethylpiperidin-1-oxyl.

Suitable acid halides for carrying out steps 2 and 5 of process P2 according to the invention are in each case all organic or inorganic acid halides which are customary for such reactions. Preference is given to using notably phosgene, phosphorous trichloride, phosphorous pentachloride, phosphorous trichloride oxide, thionyl chloride, or carbon tetrachloride-triphenylphosphine.

Suitable fluorinating agent for carrying out step 3 of process P2 according to the invention is in each case all fluorinating agents which are customary for such reactions. Preference is given to using cesium fluoride, potassium fluoride, potassium fluoride-calcium difluoride, or tetrabutylammonium fluoride.

When carrying out steps 1 to 5 of process P2 according to the invention, the reaction temperatures can independently be varied within a relatively wide range. Generally, processes according to the invention are carried out at temperatures between 0° C. and 160° C., preferably between 10° C. and 120° C. A way to control the temperature for the processes according to the invention is to use the micro-waves technology.

Steps 1 to 5 of process P2 according to the invention are generally independently carried out under atmospheric pressure. However, in each case, it is also possible to operate under elevated or reduced pressure.

When carrying out step 1 of process P2 according to the invention, generally one mole or other an excess of the oxidant is employed per mole of aldehyde of formula (IV). It is also possible to employ the reaction components in other ratios.

When carrying out carrying out steps 2 and 5 of process P2 to the invention, generally one mole or other an excess of the acid halides is employed per mole of acid of formula (IIIa) or (IIId). It is also possible to employ the reaction components in other ratios.

When carrying out steps 3 of process P2 according to the invention generally one mole or other an excess of fluorinating agent is employed per mole of acid chloride (IIIb). It is also possible to employ the reaction components in other ratios.

When carrying out steps 4 of process P2 according to the invention generally one mole or other an excess of acid or base is employed per mole of acid fluoride (IIIc). It is also possible to employ the reaction components in other ratios.

According to a further aspect according to the invention, there is provided a process P3 for the preparation of a compound of formula (I) wherein T represents S, starting from a compound of formula (I) wherein T represents O and illustrated according to the following reaction scheme:

wherein X¹, X², Y, Z¹, Z², Z³, W and B are as herein-defined, in the optional presence of a catalytic or stoechiometric or more, quantity of a base such as an inorganic and organic base. Preference is given to using alkali metal carbonates, such as sodium carbonate, potassium carbonate, potassium bicarbonate, sodium bicarbonate; heterocyclic aromatic bases, such as pyridine, picoline, lutidine, collidine; and also tertiary amines, such as trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, N,N-dimethyl-aminopyridine or N-methyl-piperidine.

Process P3 according to the invention is performed in the presence of a thionating agent.

Starting amide derivatives of formula (I) can be prepared according to processes P1.

Suitable thionating agents for carrying out process P3 according to the invention can be sulphur (S), sulfhydric acid (H₂S), sodium sulfide (Na₂S), sodium hydrosulfide (NaHS), boron trisulfide (B₂S₃), bis(diethylaluminium) sulfide ((AlEt₂)₂S), ammonium sulfide ((NH₄)₂S), phosphorous pentasulfide (P₂S₅), Lawesson's reagent (2,4-bis(4-methoxyphenyl)-1,2,3,4-dithiadiphosphetane 2,4-disulfide) or a polymer-supported thionating reagent such as described in Journal of the Chemical Society, Perkin 1 (2001), 358.

The compound according to the present invention can be prepared according to the general processes of preparation described above. It will nevertheless be understood that, on the basis of his general knowledge and of available publications, the skilled worker will be able to adapt this method according to the specifics of each of the compounds, which it is desired to synthesize.

In a further aspect, the present invention also relates to a fungicide composition comprising an effective and non-phytotoxic amount of an active compound of formula (I).

The expression “effective and non-phytotoxic amount” means an amount of composition according to the invention that is sufficient to control or destroy the fungi present or liable to appear on the cropsand that does not entail any appreciable symptom of phytotoxicity for the said crops. Such an amount can vary within a wide range depending on the fungus to be controlled, the type of crop, the climatic conditions and the compounds included in the fungicide composition according to the invention. This amount can be determined by systematic field trials that are within the capabilities of a person skilled in the art.

Thus, according to the invention, there is provided a fungicide composition comprising, as an active ingredient, an effective amount of a compound of formula (I) as herein defined and an agriculturally acceptable support, carrier or filler.

According to the invention, the term “support” denotes a natural or synthetic, organic or inorganic compound with that the active compound of formula (I) is combined or associated to make it easier to apply, notably to the parts of the plant. This support is thus generally inert and should be agriculturally acceptable. The support can be a solid or a liquid. Examples of suitable supports include clays, natural or synthetic silicates, silica, resins, waxes, solid fertilisers, water, alcohols, in particular butanol, organic solvents, mineral and plant oils and derivatives thereof. Mixtures of such supports can also be used.

The composition according to the invention can also comprise additional components. In particular, the composition can further comprise a surfactant. The surfactant can be an emulsifier, a dispersing agent or a wetting agent of ionic or non-ionic type or a mixture of such surfactants. Mention can be made, for example, of polyacrylic acid salts, lignosulphonic acid salts, phenolsulphonic or naphthalenesulphonic acid salts, polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines, substituted phenols (in particular alkylphenols or arylphenols), salts of sulphosuccinic acid esters, taurine derivatives (in particular alkyl taurates), phosphoric esters of polyoxyethylated alcohols or phenols, fatty acid esters of polyolsand derivatives of the above compounds containing sulphate, sulphonate and phosphate functions. The presence of at least one surfactant is generally essential when the active to compound and/or the inert support are water-insoluble and when the vector agent for the application is water. Preferably, surfactant content can be comprised from 5% to 40% by weight of the composition.

Optionally, additional components can also be included, e.g. protective colloids, adhesives, thickeners, thixotropic agents, penetration agents, stabilisers, sequestering agents. More generally, the active compounds can be combined with any solid or liquid additive, that complies with the usual formulation techniques.

In general, the composition according to the invention can contain from 0.05 to 99% by weight of active compound, preferably 10 to 70% by weight.

Compositions according to the invention can be used in various forms such as aerosol dispenser, capsule suspension, cold fogging concentrate, dustable powder, emulsifiable concentrate, emulsion oil in water, emulsion water in oil, encapsulated granule, fine granule, flowable concentrate for seed treatment, gas (under pressure), gas generating product, granule, hot fogging concentrate, macrogranule, microgranule, oil dispersible powder, oil miscible flowable concentrate, oil miscible liquid, paste, plant rodlet, powder for dry seed treatment, seed coated with a pesticide, soluble concentrate, soluble powder, solution for seed treatment, suspension concentrate (flowable concentrate), ultra low volume (ULV) liquid, ultra low volume (ULV) suspension, water dispersible granules or tablets, water dispersible powder for slurry treatment, water soluble granules or tablets, water soluble powder for seed treatment and wettable powder. These compositions include not only compositions that are ready to be applied to the plant or seed to be treated by means of a suitable device, such as a spraying or dusting device, but also concentrated commercial compositions that must be diluted before application to the crop.

The compounds according to the invention can also be mixed with one or more insecticide, fungicide, bactericide, attractant, acaricide or pheromone active substance or other compounds with biological activity. The mixtures thus obtained have normally a broadened spectrum of activity. The mixtures with other fungicide compounds are particularly advantageous.

Examples of suitable fungicide mixing partners can be selected in the following lists:

(1) Inhibitors of the ergosterol biosynthesis, for example (1.1) aldimorph (1704-28-5), (1.2) azaconazole (60207-31-0), (1.3) bitertanol (55179-31-2), (1.4) bromuconazole (116255-48-2), (1.5) cyproconazole (113096-99-4), (1.6) diclobutrazole (75736-33-3), (1.7) difenoconazole (119446-68-3), (1.8) diniconazole (83657-24-3), (1.9) diniconazole-M (83657-18-5), (1.10) dodemorph (1593-77-7), (1.11) dodemorph acetate (31717-87-0), (1.12) epoxiconazole (106325-08-0), (1.13) etaconazole (60207-93-4), (1.14) fenarimol (60168-88-9), (1.15) fenbuconazole (114369-43-6), (1.16) fenhexamid (126833-17-8), (1.17) fenpropidin (67306-00-7), (1.18) fenpropimorph (67306-03-0), (1.19) fluquinconazole (136426-54-5), (1.20) flurprimidol (56425-91-3), (1.21) flusilazole (85509-19-9), (1.22) flutriafol (76674-21-0), (1.23) furconazole (112839-33-5), (1.24) furconazole-cis (112839-32-4), (1.25) hexaconazole (79983-71-4), (1.26) imazalil (60534-80-7), (1.27) imazalil sulfate (58594-72-2), (1.28) imibenconazole (86598-92-7), (1.29) ipconazole (125225-28-7), (1.30) metconazole (125116-23-6), (1.31) myclobutanil (88671-89-0), (1.32) naftifine (65472-88-0), (1.33) nuarimol (63284-71-9), (1.34) oxpoconazole (174212-12-5), (1.35) to paclobutrazol (76738-62-0), (1.36) pefurazoate (101903-30-4), (1.37) penconazole (66246-88-6), (1.38) piperalin (3478-94-2), (1.39) prochloraz (67747-09-5), (1.40) propiconazole (60207-90-1), (1.41) prothioconazole (178928-70-6), (1.42) pyributicarb (88678-67-5), (1.43) pyrifenox (88283-41-4), (1.44) quinconazole (103970-75-8), (1.45) simeconazole (149508-90-7), (1.46) spiroxamine (118134-30-8), (1.47) tebuconazole (107534-96-3), (1.48) terbinafine (91161-71-6), (1.49) tetraconazole (112281-77-3), (1.50) triadimefon (43121-43-3), (1.51) triadimenol (89482-17-7), (1.52) tridemorph (81412-43-3), (1.53) triflumizole (68694-11-1), (1.54) triforine (26644-46-2), (1.55) triticonazole (131983-72-7), (1.56) uniconazole (83657-22-1), (1.57) uniconazole-p (83657-17-4), (1.58) viniconazole (77174-66-4), (1.59) voriconazole (137234-62-9), (1.60) 1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)cycloheptanol (129586-32-9), (1.61) methyl 1-(2,2-dimethyl-2,3-dihydro-1H-inden-1-yl)-1H-imidazole-5-carboxylate (110323-95-0), (1.62) N′-{5-(difluoromethyl)-2-methyl-4-[3-(trimethylsilyl)propoxy]phenyl}-N-ethyl-N-methylimidoformamide, (1.63) N-ethyl-N-methyl-N′-{2-methyl-5-(trifluoromethyl)-4-[3-(trimethylsilyl)propoxy]phenyl}imidoformamide and (1.64) O-[1-(4-methoxyphenoxy)-3,3-dimethylbutan-2-yl] 1H-imidazole-1-carbothioate (111226-71-2). (2) inhibitors of the respiratory chain at complex I or II, for example (2.1) bixafen (581809-46-3), (2.2) boscalid (188425-85-6), (2.3) carboxin (5234-68-4), (2.4) diflumetorim (130339-07-0), (2.5) fenfuram (24691-80-3), (2.6) fluopyram (658066-35-4), (2.7) flutolanil (66332-96-5), (2.8) fluxapyroxad (907204-31-3), (2.9) furametpyr (123572-88-3), (2.10) furmecyclox (60568-05-0), (2.11) isopyrazam (mixture of syn-epimeric racemate 1 RS,4SR,9RS and anti-epimeric racemate 1 RS,4SR,9SR) (881685-58-1), (2.12) isopyrazam (anti-epimeric racemate 1RS,4SR,9SR), (2.13) isopyrazam (anti-epimeric enantiomer 1R,4S,9S), (2.14) isopyrazam (anti-epimeric enantiomer 1S,4R,9R), (2.15) isopyrazam (syn epimeric racemate 1 RS,4SR,9RS), (2.16) isopyrazam (syn-epimeric enantiomer 1R,4S,9R), (2.17) isopyrazam (syn-epimeric enantiomer 1S,4R,9S), (2.18) mepronil (55814-41-0), (2.19) oxycarboxin (5259-88-1), (2.20) penflufen (494793-67-8), (2.21) penthiopyrad (183675-82-3), (2.22) sedaxane (874967-67-6), (2.23) thifluzamide (130000-40-7), (2.24) 1-methyl-N-[2-(1,1,2,2-tetrafluoroethoxy)phenyl]-3-(trifluoromethyl)-1H-pyrazole-4-carboxamide, (2.25) 3-(difluoromethyl)-1-methyl-N-[2-(1,1,2,2-tetrafluoroethoxy)phenyl]-1H-pyrazole-4-carboxamide, (2.26) 3-(difluoromethyl)-N-[4-fluoro-2-(1,1,2,3,3,3-hexafluoropropoxy)phenyl]-1-methyl-1H-pyrazole-4-carboxamide, (2.27) N-[1-(2,4-dichlorophenyl)-1-methoxypropan-2-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide (1092400-95-7) (WO 2008148570), (2.28) 5,8-difluoro-N-[2-(2-fluoro-4-{[4-(trifluoromethyl)pyridin-2-yl]oxy}phenyl)ethyl]quinazolin-4-amine (1210070-84-0) (WO2010025451) and (2.29) N-[9-(dichloromethylene)-1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide. (3) inhibitors of the respiratory chain at complex III, for example (3.1) ametoctradin (865318-97-4), (3.2) amisulbrom (348635-87-0), (3.3) azoxystrobin (131860-33-8), (3.4) cyazofamid (120116-88-3), (3.5) coumethoxystrobin (850881-30-0), (3.6) coumoxystrobin (850881-70-8), (3.7) dimoxystrobin (141600-52-4), (3.8) enestroburin (238410-11-2) (WO 2004/058723), (3.9) famoxadone (131807-57-3) (WO 2004/058723), (3.10) fenamidone (161326-34-7) (WO 2004/058723), (3.11) fenoxystrobin (918162-02-4), (3.12) fluoxastrobin (361377-29-9) (WO 2004/058723), (3.13) kresoxim-methyl (143390-89-0) (WO 2004/058723), (3.14) metominostrobin (133408-50-1) (WO 2004/058723), (3.15) orysastrobin (189892-69-1) (WO 2004/058723), (3.16) picoxystrobin (117428-22-5) (WO 2004/058723), (3.17) pyraclostrobin (175013-18-0) (WO 2004/058723), (3.18) pyrametostrobin (915410-70-7) (WO 2004/058723), (3.19) pyraoxystrobin (862588-11-2) (WO 2004/058723), (3.20) pyribencarb (799247-52-2) (WO 2004/058723), (3.21) triclopyricarb (902760-40-1), (3.22) trifloxystrobin (141517-21-7) (WO 2004/058723), (3.23) (2E)-2-(2-{[6-(3-chloro-2-methylphenoxy)-5-fluoropyrimidin-4-yl]oxy}phenyl)-2-(methoxyimino)-N-methylethanamide (WO 2004/058723), (3.24) (2E)-2-(methoxyimino)-N-methyl-2-(2-{[({(1E)-1-[3-(trifluoromethyl)phenyl]ethylidene}amino)oxy]methyl}phenyl)ethanamide (WO 2004/058723), (3.25) (2E)-2-(methoxyimino)-N-methyl-2-{2-[(E)-({1-[3-(trifluoromethyl)phenyl]ethoxy}imino)methyl]phenyl}ethanamide (158169-73-4), (3.26) (2E)-2-{2-[({[(1E)-1-(3-{[(E)-1-fluoro-2-phenylethenyl]oxy}phenyl)ethylidene]amino}oxy)methyl]phenyl}-2-(methoxyimino)-N-methylethanamide (326896-28-0), (3.27) (2E)-2-{2-[({[(2E,3E)-4-(2,6-dichlorophenyl)but-3-en-2-ylidene]amino}oxy)methyl]phenyl}-2-(methoxyimino)-N-methylethanamide, (3.28) 2-chloro-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)pyridine-3-carboxamide (119899-14-8), (3.29) 5-methoxy-2-methyl-4-(2-{[({(1E)-1-[3-(trifluoromethyl)phenyl]ethylidene}amino)oxy]methyl}phenyl)-2,4-dihydro-3H-1,2,4-triazol-3-one, (3.30) methyl (2E)-2-{2-[({cyclopropyl[(4-methoxyphenyl)imino]methyl}sulfanyl)methyl]phenyl}-3-methoxyprop-2-enoate (149601-03-6), (3.31) N-(3-ethyl-3,5,5-trimethylcyclohexyl)-3-(formylamino)-2-hydroxybenzamide (226551-21-9), (3.32) 2-{2-[(2,5-dimethylphenoxy)methyl]phenyl}-2-methoxy-N-methylacetamide (173662-97-0) and (3.33) (2R)-2-{2-[(2,5-dimethylphenoxy)methyl]phenyl}-2-methoxy-N-methylacetamide (394657-24-0). (4) Inhibitors of the mitosis and cell division, for example (4.1) benomyl (17804-35-2), (4.2) carbendazim (10605-21-7), (4.3) chlorfenazole (3574-96-7), (4.4) diethofencarb (87130-20-9), (4.5) ethaboxam (162650-77-3), (4.6) fluopicolide (239110-15-7), (4.7) fuberidazole (3878-19-1), (4.8) pencycuron (66063-05-6), (4.9) thiabendazole (148-79-8), (4.10) thiophanate-methyl (23564-05-8), (4.11) thiophanate (23564-06-9), (4.12) zoxamide (156052-68-5), (4.13) 5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)[1,2,4]triazolo[1,5-a]pyrimidine (214706-53-3) and (4.14) 3-chloro-5-(6-chloropyridin-3-yl)-6-methyl-4-(2,4,6-trifluorophenyl)pyridazine (1002756-87-7). (5) Compounds capable to have a multisite action, like for example (5.1) bordeaux mixture (8011-63-0), (5.2) captafol (2425-06-1), (5.3) captan (133-06-2) (WO 02/12172), (5.4) chlorothalonil (1897-45-6), (5.5) copper hydroxide (20427-59-2), (5.6) copper naphthenate (1338-02-9), (5.7) copper oxide (1317-39-1), (5.8) copper oxychloride (1332-40-7), (5.9) copper(2+) sulfate (7758-98-7), (5.10) dichlofluanid (1085-98-9), (5.11) dithianon (3347-22-6), (5.12) dodine (2439-10-3), (5.13) dodine free base, (5.14) ferbam (14484-64-1), (5.15) fluorofolpet (719-96-0), (5.16) folpet (133-07-3), (5.17) guazatine (108173-90-6), (5.18) guazatine acetate, (5.19) iminoctadine (13516-27-3), (5.20) iminoctadine albesilate (169202-06-6), (5.21) iminoctadine triacetate (57520-17-9), (5.22) mancopper (53988-93-5), (5.23) mancozeb (8018-01-7), (5.24) maneb (12427-38-2), (5.25) metiram (9006-42-2), (5.26) metiram zinc (9006-42-2), (5.27) oxine-copper (10380-28-6), (5.28) propamidine (104-32-5), (5.29) propineb (12071-83-9), (5.30) sulphur and sulphur preparations including calcium polysulphide (7704-34-9), (5.31) thiram (137-26-8), (5.32) tolylfluanid (731-27-1), (5.33) zineb (12122-67-7) and (5.34) ziram (137-30-4). (6) Compounds capable to induce a host defence, like for example (6.1) acibenzolar-S-methyl (135158-54-2), (6.2) isotianil (224049-04-1), (6.3) probenazole (27605-76-1) and (6.4) tiadinil (223580-51-6). (7) Inhibitors of the amino acid and/or protein biosynthesis, for example (7.1) andoprim (23951-85-1), (7.2) blasticidin-S (2079-00-7), (7.3) cyprodinil (121552-61-2), (7.4) kasugamycin (6980-18-3), (7.5) kasugamycin hydrochloride hydrate (19408-46-9), (7.6) mepanipyrim (110235-47-7), (7.7) pyrimethanil (53112-28-0) and (7.8) 3-(5-fluoro-3,3,4,4-tetramethyl-3,4-dihydroisoquinolin-1-yl)quinoline (861647-32-7) (WO2005070917). (8) Inhibitors of the ATP production, for example (8.1) fentin acetate (900-95-8), (8.2) fentin chloride (639-58-7), (8.3) fentin hydroxide (76-87-9) and (8.4) silthiofam (175217-20-6). (9) Inhibitors of the cell wall synthesis, for example (9.1) benthiavalicarb (177406-68-7), (9.2) dimethomorph (110488-70-5), (9.3) flumorph (211867-47-9), (9.4) iprovalicarb (140923-17-7), (9.5) mandipropamid (374726-62-2), (9.6) polyoxins (11113-80-7), (9.7) polyoxorim (22976-86-9), (9.8) validamycin A (37248-47-8) and (9.9) valifenalate (283159-94-4; 283159-90-0). (10) Inhibitors of the lipid and membrane synthesis, for example (10.1) biphenyl (92-52-4), (10.2) chloroneb (2675-77-6), (10.3) dicloran (99-30-9), (10.4) edifenphos (17109-49-8), (10.5) etridiazole (2593-15-9), (10.6) iodocarb (55406-53-6), (10.7) iprobenfos (26087-47-8), (10.8) isoprothiolane (50512-35-1), (10.9) propamocarb (25606-41-1), (10.10) propamocarb hydrochloride (25606-41-1), (10.11) prothiocarb (19622-08-3), (10.12) pyrazophos (13457-18-6), (10.13) quintozene (82-68-8), (10.14) tecnazene (117-18-0) and (10.15) tolclofos-methyl (57018-04-9). (11) Inhibitors of the melanine biosynthesis, for example (11.1) carpropamid (104030-54-8), (11.2) diclocymet (139920-32-4), (11.3) fenoxanil (115852-48-7), (11.4) phthalide (27355-22-2), (11.5) pyroquilon (57369-32-1), (11.6) tricyclazole (41814-78-2) and (11.7) 2,2,2-trifluoroethyl {3-methyl-1-[(4-methylbenzoyl)amino]butan-2-yl}carbamate (851524-22-6) (WO2005042474). (12) Inhibitors of the nucleic acid synthesis, for example (12.1) benalaxyl (71626-11-4), (12.2) benalaxyl-M (kiralaxyl) (98243-83-5), (12.3) bupirimate (41483-43-6), (12.4) clozylacon (67932-85-8), (12.5) dimethirimol (5221-53-4), (12.6) ethirimol (23947-60-6), (12.7) furalaxyl (57646-30-7), (12.8) hymexazol (10004-44-1), (12.9) metalaxyl (57837-19-1), (12.10) metalaxyl-M (mefenoxam) (70630-17-0), (12.11) ofurace (58810-48-3), (12.12) oxadixyl (77732-09-3) and (12.13) oxolinic acid (14698-29-4). (13) Inhibitors of the signal transduction, for example (13.1) chlozolinate (84332-86-5), (13.2) fenpiclonil (74738-17-3), (13.3) fludioxonil (131341-86-1), (13.4) iprodione (36734-19-7), (13.5) procymidone (32809-16-8), (13.6) quinoxyfen (124495-18-7) and (13.7) vinclozolin (50471-44-8). (14) Compounds capable to act as an uncoupler, like for example (14.1) binapacryl (485-31-4), (14.2) dinocap (131-72-6), (14.3) ferimzone (89269-64-7), (14.4) fluazinam (79622-59-6) and (14.5) meptyldinocap (131-72-6). (15) Further compounds, like for example (15.1) benthiazole (21564-17-0), (15.2) bethoxazin (163269-30-5), (15.3) capsimycin (70694-08-5), (15.4) carvone (99-49-0), (15.5) chinomethionat (2439-01-2), (15.6) pyriofenone (chlazafenone) (688046-61-9), (15.7) cufraneb (11096-18-7), (15.8) cyflufenamid (180409-60-3), (15.9) cymoxanil (57966-95-7), (15.10) cyprosulfamide (221667-31-8), (15.11) dazomet (533-74-4), (15.12) debacarb (62732-91-6), (15.13) dichlorophen (97-23-4), (15.14) diclomezine (62865-36-5), (15.15) difenzoquat (49866-87-7), (15.16) difenzoquat methylsulphate (43222-48-6), (15.17) diphenylamine (122-39-4), (15.18) ecomate, (15.19) fenpyrazamine (473798-59-3), (15.20) flumetover (154025-04-4), (15.21) fluoroimide (41205-21-4), (15.22) flusulfamide (106917-52-6), (15.23) flutianil (304900-25-2), (15.24) fosetyl-aluminium (39148-24-8), (15.25) fosetyl-calcium, (15.26) fosetyl-sodium (39148-16-8), (15.27) hexachlorobenzene (118-74-1), (15.28) irumamycin (81604-73-1), (15.29) methasulfocarb (66952-49-6), (15.30) methyl isothiocyanate (556-61-6), (15.31) metrafenone (220899-03-6), (15.32) mildiomycin (67527-71-3), (15.33) natamycin (7681-93-8), (15.34) nickel dimethyldithiocarbamate (15521-65-0), (15.35) nitrothal-isopropyl (10552-74-6), (15.36) octhilinone (26530-20-1), (15.37) oxamocarb (917242-12-7), (15.38) oxyfenthiin (34407-87-9), (15.39) pentachlorophenol and salts (87-86-5), (15.40) phenothrin, (15.41) phosphorous acid and its salts (13598-36-2), (15.42) propamocarb-fosetylate, (15.43) propanosine-sodium (88498-02-6), (15.44) proquinazid (189278-12-4), (15.45) pyrimorph (868390-90-3), (15.46) pyrroInitrine (1018-71-9) (EP-A 1 559 320), (15.47) tebufloquin (376645-78-2), (15.48) tecloftalam (76280-91-6), (15.49) tolnifanide (304911-98-6), (15.50) triazoxide (72459-58-6), (15.51) trichlamide (70193-21-4), (15.52) zarilamid (84527-51-5), (15.53) (3S,6S,7R,8R)-8-benzyl-3-[({3-[(isobutyryloxy)methoxy]-4-methoxypyridin-2-yl}carbonyl)amino]-6-methyl-4,9-dioxo-1,5-dioxonan-7-yl 2-methylpropanoate (517875-34-2) (WO2003035617), (15.54) 1-(4-{4-[(5R)-5-(2,6-difluorophenyl)-4,5-dihydro-1,2-oxazol-3-yl]-1,3-thiazol-2-yl}piperidin-1-yl)-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone (1003319-79-6) (WO 2008013622), (15.55) 1-(4-{4-[(5S)-5-(2,6-difluorophenyl)-4,5-dihydro-1,2-oxazol-3-yl]-1,3-thiazol-2-yl}piperidin-1-yl)-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone (1003319-80-9) (WO 2008013622), (15.56) 1-(4-{4-[5-(2,6-difluorophenyl)-4,5-dihydro-1,2-oxazol-3-yl]-1,3-thiazol-2-yl}piperidin-1-yl)-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone (1003318-67-9) (WO 2008013622), (15.57) 1-(4-methoxyphenoxy)-3,3-dimethylbutan-2-yl 1H-imidazole-1-carboxylate (111227-17-9), (15.58) 2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine (13108-52-6), (15.59) 2,3-dibutyl-6-chlorothieno[2,3-d]pyrimidin-4(3H)-one (221451-58-7), (15.60) 2,6-dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c′]dipyrrole-1,3,5,7(2H,6H)-tetrone, (15.61) 2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]-1-(4-{4-[(5R)-5-phenyl-4,5-dihydro-1,2-oxazol-3-yl]-1,3-thiazol-2-yl}piperidin-1-yl)ethanone (1003316-53-7) (WO 2008013622), (15.62) 2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]-1-(4-{4-[(5S)-5-phenyl-4,5-dihydro-1,2-oxazol-3-yl]-1,3-thiazol-2-yl}piperidin-1-yl)ethanone (1003316-54-8) (WO 2008013622), (15.63) 2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]-1-{4-[4-(5-phenyl-4,5-dihydro-1,2-oxazol-3-yl)-1,3-thiazol-2-yl]piperidin-1-yl}ethanone (1003316-51-5) (WO 2008013622), (15.64) 2-butoxy-6-iodo-3-propyl-4H-chromen-4-one, (15.65) 2-chloro-5-[2-chloro-1-(2,6-difluoro-4-methoxyphenyl)-4-methyl-1H-imidazol-5-yl]pyridine, (15.66) 2-phenylphenol and salts (90-43-7), (15.67) 3-(4,4,5-trifluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1-yl)quinoline (861647-85-0) (WO2005070917), (15.68) 3,4,5-trichloropyridine-2,6-dicarbonitrile (17824-85-0), (15.69) 3-[5-(4-chlorophenyl)-2,3-dimethyl-1,2-oxazolidin-3-yl]pyridine, (15.70) 3-chloro-5-(4-chlorophenyl)-4-(2,6-difluorophenyl)-6-methylpyridazine, (15.71) 4-(4-chlorophenyl)-5-(2,6-difluorophenyl)-3,6-dimethylpyridazine, (15.72) 5-amino-1,3,4-thiadiazole-2-thiol, (15.73) 5-chloro-N′-phenyl-N′-(prop-2-yn-1-yl)thiophene-2-sulfonohydrazide (134-31-6), (15.74) 5-fluoro-2-[(4-fluorobenzyl)oxy]pyrimidin-4-amine (1174376-11-4) (WO2009094442), (15.75) 5-fluoro-2-[(4-methylbenzyl)oxy]pyrimidin-4-amine (1174376-25-0) (WO2009094442), (15.76) 5-methyl-6-octyl[1,2,4]triazolo[1,5-a]pyrimidin-7-amine, (15.77) ethyl (2Z)-3-amino-2-cyano-3-phenylprop-2-enoate, (15.78) N′-(4-{[3-(4-chlorobenzyl)-1,2,4-thiadiazol-5-yl]oxy}-2,5-dimethylphenyl)-N-ethyl-N-methylimidoformamide, (15.79) N-(4-chlorobenzyl)-3-[3-methoxy-4-(prop-2-yn-1-yloxy)phenyl]propanamide, (15.80) N-[(4-chlorophenyl)(cyano)methyl]-3-[3-methoxy-4-(prop-2-yn-1-yloxy)phenyl]propanamide, (15.81) N-[(5-bromo-3-chloropyridin-2-yl)methyl]-2,4-dichloropyridine-3-carboxamide, (15.82) N-[1-(5-bromo-3-chloropyridin-2-yl)ethyl]-2,4-dichloropyridine-3-carboxamide, (15.83) N-[1-(5-bromo-3-chloropyridin-2-yl)ethyl]-2-fluoro-4-iodopyridine-3-carboxamide, (15.84) N-{(E)-[(cyclopropylmethoxy)imino][6-(difluoromethoxy)-2,3-difluorophenyl]methyl}-2-phenylacetamide (221201-92-9), (15.85) N-{(Z)-[(cyclopropylmethoxy)imino][6-(difluoromethoxy)-2,3-difluorophenyl]methyl}-2-phenylacetamide (221201-92-9), (15.86) N′-{4-[(3-tert-butyl-4-cyano-1,2-thiazol-5-yl)oxy]-2-chloro-5-methylphenyl}-N-ethyl-N-methylimidoformamide, (15.87) N-methyl-2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-N-(1,2,3,4-tetrahydronaphthalen-1-yl)-1,3-thiazole-4-carboxamide (922514-49-6) (WO 2007014290), (15.88) N-methyl-2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-N-[(1R)-1,2,3,4-tetrahydronaphthalen-1-yl]-1,3-thiazole-4-carboxamide (922514-07-6) (WO 2007014290), (15.89) N-methyl-2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-N-[(1S)-1,2,3,4-tetrahydronaphthalen-1-yl]-1,3-thiazole-4-carboxamide (922514-48-5) (WO 2007014290), (15.90) pentyl {6-[({[(1-methyl-1H-tetrazol-5-yl)(phenyl)methylidene]amino}oxy)methyl]pyridin-2-yl}carbamate, (15.91) phenazine-1-carboxylic acid, (15.92) quinolin-8-ol (134-31-6), (15.93) quinolin-8-ol sulfate (2:1) (134-31-6) and (15.94) tert-butyl {6-[({[(1-methyl-1H-tetrazol-5-yl)(phenyl)methylene]amino}oxy)methyl]pyridin-2-yl}carbamate. (16) Further compounds, like for example (16.1) 1-methyl-3-(trifluoromethyl)-N-[2′-(trifluoromethyl)biphenyl-2-yl]-1H-pyrazole-4-carboxamide, (16.2) N-(4′-chlorobiphenyl-2-yl)-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, (16.3) N-(2′,4′-dichlorobiphenyl-2-yl)-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, (16.4) 3-(difluoromethyl)-1-methyl-N-[4′-(trifluoromethyl)biphenyl-2-yl]-1H-pyrazole-4-carboxamide, (16.5) N-(2′,5′-difluorobiphenyl-2-yl)-1-methyl-3-(trifluoromethyl)-1H-pyrazole-4-carboxamide, (16.6) 3-(difluoromethyl)-1-methyl-N-[4′-(prop-1-yn-1-yl)biphenyl-2-yl]-1H-pyrazole-4-carboxamide (known from WO 2004/058723), (16.7) 5-fluoro-1,3-dimethyl-N-[4′-(prop-1-yn-1-yl)biphenyl-2-yl]-1H-pyrazole-4-carboxamide (known from WO 2004/058723), (16.8) 2-chloro-N-[4′-(prop-1-yn-1-yl)biphenyl-2-yl]pyridine-3-carboxamide (known from WO 2004/058723), (16.9) 3-(difluoromethyl)-N-[4′-(3,3-dimethylbut-1-yn-1-yl)biphenyl-2-yl]-1-methyl-1H-pyrazole-4-carboxamide (known from WO 2004/058723), (16.10) N-[4′-(3,3-dimethylbut-1-yn-1-yl)biphenyl-2-yl]-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide (known from WO 2004/058723), (16.11) 3-(difluoromethyl)-N-(4′-ethynylbiphenyl-2-yl)-1-methyl-1H-pyrazole-4-carboxamide (known from WO 2004/058723), (16.12) N-(4′-ethynylbiphenyl-2-yl)-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide (known from WO 2004/058723), (16.13) 2-chloro-N-(4′-ethynylbiphenyl-2-yl)pyridine-3-carboxamide (known from WO 2004/058723), (16.14) 2-chloro-N-[4′-(3,3-dimethylbut-1-yn-1-yl)biphenyl-2-yl]pyridine-3-carboxamide (known from WO 2004/058723), (16.15) 4-(difluoromethyl)-2-methyl-N-[4′-(trifluoromethyl)biphenyl-2-yl]-1,3-thiazole-5-carboxamide (known from WO 2004/058723), (16.16) 5-fluoro-N-[4′-(3-hydroxy-3-methylbut-1-yn-1-yl)biphenyl-2-yl]-1,3-dimethyl-1H-pyrazole-4-carboxamide (known from WO 2004/058723), (16.17) 2-chloro-N-[4′-(3-hydroxy-3-methylbut-1-yn-1-yl)biphenyl-2-yl]pyridine-3-carboxamide (known from WO 2004/058723), (16.18) 3-(difluoromethyl)-N-[4′-(3-methoxy-3-methylbut-1-yn-1-yl)biphenyl-2-yl]-1-methyl-1H-pyrazole-4-carboxamide (known from WO 2004/058723), (16.19) 5-fluoro-N-[4′-(3-methoxy-3-methylbut-1-yn-1-yl)biphenyl-2-yl]-1,3-dimethyl-1H-pyrazole-4-carboxamide (known from WO 2004/058723), (16.20) 2-chloro-N-[4′-(3-methoxy-3-methylbut-1-yn-1-yl)biphenyl-2-yl]pyridine-3-carboxamide (known from WO 2004/058723), (16.21) (5-bromo-2-methoxy-4-methylpyridin-3-yl)(2,3,4-trimethoxy-6-methylphenyl)methanone (known from EP-A 1 559 320) and (16.22) N-[2-(4-{[3-(4-chlorophenyl)prop-2-yn-1-yl]oxy}-3-methoxyphenyl)ethyl]-N-2-(methylsulfonyl)valinamide (220706-93-4).

All named mixing partners of the classes (1) to (16) can, if their functional groups enable this, optionally form salts with suitable bases or acids.

The composition according to the invention comprising a mixture of a compound of formula (I) with a bactericide compound can also be particularly advantageous. Examples of suitable bactericide mixing partners can be selected in the following list: bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone, furancarboxylic acid, oxytetracycline, probenazole, streptomycin, tecloftalam, copper sulphate and other copper preparations.

The compounds of formula (I) and the fungicide composition according to the invention can be used to curatively or preventively control the phytopathogenic fungi of plants or crops.

Thus, according to a further aspect of the invention, there is provided a method for curatively or preventively controlling the phytopathogenic fungi of plants or crops characterised in that a compound of formula (I) or a fungicide composition according to the invention is applied to the seed, the plant or to the fruit of the plant or to the soil wherein the plant is growing or wherein it is desired to grow.

The method of treatment according to the invention can also be useful to treat propagation material such as tubers or rhizomes, but also seeds, seedlings or seedlings pricking out and plants or plants pricking out. This method of treatment can also be useful to treat roots. The method of treatment according to the invention can also be useful to treat the overground parts of the plant such as trunks, stems or stalks, leaves, flowers and fruit of the concerned plant.

According to the invention all plants and plant parts can be treated. By plants is meant all plants and plant populations such as desirable and undesirable wild plants, cultivars and plant varieties (whether or not protectable by plant variety or plant breeder's rights). Cultivars and plant varieties can be plants obtained by conventional propagation and breeding methods which can be assisted or supplemented by one or more biotechnological methods such as by use of double haploids, protoplast fusion, random and directed mutagenesis, molecular or genetic markers or by bioengineering and genetic engineering methods. By plant parts is meant all above ground and below ground parts and organs of plants such as shoot, leaf, blossom and root, whereby for example leaves, needles, stems, branches, blossoms, fruiting bodies, fruits and seed as well as roots, corms and rhizomes are listed. Crops and vegetative and to generative propagating material, for example cuttings, corms, rhizomes, runners and seeds also belong to plant parts.

Among the plants that can be protected by the method according to the invention, mention may be made of major field crops like corn, soybean, cotton, Brassica oilseeds such as Brassica napus (e.g. canola), Brassica rapa, B. juncea (e.g. mustard) and Brassica carinata, rice, wheat, sugarbeet, sugarcane, oats, rye, barley, millet, triticale, flax, vine and various fruits and vegetables of various botanical taxa such as Rosaceae sp. (for instance pip fruit such as apples and pears, but also stone fruit such as apricots, cherries, almonds and peaches, berry fruits such as strawberries), Ribesioidae sp., Juglandaceae sp., Betulaceae sp., Anacardiaceae sp., Fagaceae sp., Moraceae sp., Oleaceae sp., Actimidaceae sp., Lauraceae sp., Musaceae sp. (for instance banana trees and plantings), Rubiaceae sp. (for instance coffee), Theaceae sp., Sterculiceae sp., Rutaceae sp. (for instance lemons, oranges and grapefruit); Solanaceae sp. (for instance tomatoes, potatoes, peppers, eggplant), Liliaceae sp., Compositiae sp. (for instance lettuce, artichoke and chicory-including root chicory, endive or common chicory), Umbeffiferae sp. (for instance carrot, parsley, celery and celeriac), Cucurbitaceae sp. (for instance cucumber—including pickling cucumber, squash, watermelon, gourds and melons), Alliaceae sp. (for instance onions and leek), Cruciferae sp. (for instance white cabbage, red cabbage, broccoli, cauliflower, brussel sprouts, pak choi, kohlrabi, radish, horseradish, cress, Chinese cabbage), Leguminosae sp. (for instance peanuts, peas and beans beans—such as climbing beans and broad beans), Chenopodiaceae sp. (for instance mangold, spinach beet, spinach, beetroots), Malvaceae (for instance okra), Asparagaceae (for instance asparagus); horticultural and forest crops; ornamental plants; as well as genetically modified homologues of these crops.

The method of treatment according to the invention can be used in the treatment of genetically modified organisms (GMOs), e.g. plants or seeds. Genetically modified plants (or transgenic plants) are plants of which a heterologous gene has been stably integrated into genome. The expression “heterologous gene” essentially means a gene which is provided or assembled outside the plant and when introduced in the nuclear, chloroplastic or mitochondrial genome gives the transformed plant new or improved agronomic or other properties by expressing a protein or polypeptide of interest or by downregulating or silencing other gene(s) which are present in the plant (using for example, antisense technology, cosuppression technology or RNA interference—RNAi-technology). A heterologous gene that is located in the genome is also called a transgene. A transgene that is defined by its particular location in the plant genome is called a transformation or transgenic event.

Depending on the plant species or plant cultivars, their location and growth conditions (soils, climate, vegetation period, diet), the treatment according to the invention may also result in superadditive (“synergistic”) effects. Thus, for example, reduced application rates and/or a widening of the activity spectrum and/or an increase in the activity of the active compounds and compositions which can be used according to the invention, better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, accelerated maturation, higher harvest yields, bigger fruits, larger plant height, greener leaf color, earlier flowering, higher quality and/or a higher nutritional value of the harvested products, higher sugar concentration within the fruits, better storage stability and/or processability of the harvested products are possible, which exceed the effects which were actually to be expected.

At certain application rates, the active compound combinations according to the invention may also have a strengthening effect in plants. Accordingly, they are also suitable for mobilizing the defense system of the plant against attack by unwanted microorganisms. This may, if appropriate, be one of the reasons of the enhanced activity of the combinations according to the invention, for example against fungi. Plant-strengthening (resistance-inducing) substances are to be understood as meaning, in the present context, those substances or combinations of substances which are capable of stimulating the defense system of plants in such a way that, when subsequently inoculated with unwanted microorganisms, the treated plants display a substantial degree of resistance to these microorganisms. In the present case, unwanted microorganisms are to be understood as meaning phytopathogenic fungi, bacteria and viruses. Thus, the substances according to the invention can be employed for protecting plants against attack by the abovementioned pathogens within a certain period of time after the treatment. The period of time within which protection is effected generally extends from 1 to 10 days, preferably 1 to 7 days, after the treatment of the plants with the active compounds.

Plants and plant cultivars which are preferably to be treated according to the invention include all plants which have genetic material which impart particularly advantageous, useful traits to these plants (whether obtained by breeding and/or biotechnological means).

Plants and plant cultivars which are also preferably to be treated according to the invention are resistant against one or more biotic stresses, i.e. said plants show a better defense against animal and microbial pests, such as against nematodes, insects, mites, phytopathogenic fungi, bacteria, viruses and/or viroids.

Examples of nematode resistant plants are described in e.g. U.S. patent application Ser. Nos. 11/765,491, 11/765,494, 10/926,819, 10/782,020, 12/032,479, 10/783,417, 10/782,096, 11/657,964, 12/192,904, 11/396,808, 12/166,253, 12/166,239, 12/166,124, 12/166,209, 11/762,886, 12/364,335, 11/763,947, 12/252,453, 12/209,354, 12/491,396 or 12/497,221.

Plants and plant cultivars which may also be treated according to the invention are those plants which are resistant to one or more abiotic stresses. Abiotic stress conditions may include, for example, drought, cold temperature exposure, heat exposure, osmotic stress, flooding, increased soil salinity, increased mineral exposure, ozone exposure, high light exposure, limited availability of nitrogen nutrients, limited availability of phosphorus nutrients, shade avoidance.

Plants and plant cultivars which may also be treated according to the invention, are those plants characterized by enhanced yield characteristics. Increased yield in said plants can be the result of, for example, improved plant physiology, growth and development, such as water use efficiency, water retention efficiency, improved nitrogen use, enhanced carbon assimilation, improved photosynthesis, increased germination efficiency and accelerated maturation. Yield can furthermore be affected by improved plant architecture (under stress and non-stress conditions), including but not limited to, early flowering, flowering control for hybrid seed production, seedling vigor, plant size, internode number and distance, root growth, seed size, fruit size, pod size, pod or ear number, seed number per pod or ear, seed mass, enhanced seed filling, reduced seed dispersal, reduced pod dehiscence and lodging resistance. Further yield traits include seed composition, such as carbohydrate content, protein content, oil content and composition, nutritional value, reduction in anti-nutritional compounds, improved processability and better storage stability.

Examples of plants with the above-mentioned traits are non-exhaustively listed in Table A.

Plants that may be treated according to the invention are hybrid plants that already express the characteristic of heterosis or hybrid vigor which results in generally higher yield, vigor, health and resistance towards biotic and abiotic stresses). Such plants are typically made by crossing an inbred male-sterile parent line (the female parent) with another inbred male-fertile parent line (the male parent). Hybrid seed is typically harvested from the male sterile plants and sold to growers. Male sterile plants can sometimes (e.g. in corn) be produced by detasseling, i.e. the mechanical removal of the male reproductive organs (or males flowers) but, more typically, male sterility is the result of genetic determinants in the plant genome. In that case, and especially when seed is the desired product to be harvested from the hybrid plants it is typically useful to ensure that male fertility in the hybrid plants is fully restored. This can be accomplished by ensuring that the male parents have appropriate fertility restorer genes which are capable of restoring the male fertility in hybrid plants that contain the genetic determinants responsible for male-sterility. Genetic determinants for male sterility may be located in the cytoplasm. Examples of cytoplasmic male sterility (CMS) were for instance described in Brassica species (WO 92/05251, WO 95/09910, WO 98/27806, WO 05/002324, WO 06/021972 and U.S. Pat. No. 6,229,072). However, genetic determinants for male sterility can also be located in the nuclear genome. Male sterile plants can also be obtained by plant biotechnology methods such as genetic engineering. A particularly useful means of obtaining male-sterile plants is described in WO 89/10396 in which, for example, a ribonuclease such as barnase is selectively expressed in the tapetum cells in the stamens. Fertility can then be restored by expression in the tapetum cells of a ribonuclease inhibitor such as barstar (e.g. WO 91/02069).

Plants or plant cultivars (obtained by plant biotechnology methods such as genetic engineering) which may be treated according to the invention are herbicide-tolerant plants, i.e. plants made tolerant to one or more given herbicides. Such plants can be obtained either by genetic transformation, or by selection of plants containing a mutation imparting such herbicide tolerance.

Herbicide-resistant plants are for example glyphosate-tolerant plants, i.e. plants made tolerant to the herbicide glyphosate or salts thereof. Plants can be made tolerant to glyphosate through different means. For example, glyphosate-tolerant plants can be obtained by transforming the plant with a gene encoding the enzyme 5-enolpyruvylshikimate-3-phosphate synthase (EPSPS). Examples of such EPSPS genes are the AroA gene (mutant CT7) of the bacterium Salmonella typhimurium (Comai et al., 1983, Science 221, 370-371), the CP4 gene of the bacterium Agrobacterium sp. (Barry et al., 1992, Curr. Topics Plant Physiol. 7, 139-145), the genes encoding a Petunia EPSPS (Shah et al., 1986, Science 233, 478-481), a Tomato EPSPS (Gasser et al., 1988, J. Biol. Chem. 263, 4280-4289), or an Eleusine EPSPS (WO 01/66704). It can also be a mutated EPSPS as described in for example EP 0837944, WO 00/66746, WO 00/66747 or WO02/26995. Glyphosate-tolerant plants can also be obtained by expressing a gene that encodes a glyphosate oxido-reductase enzyme as described in U.S. Pat. Nos. 5,776,760 and 5,463,175. Glyphosate-tolerant plants can also be obtained by expressing a gene that encodes a to glyphosate acetyl transferase enzyme as described in for example WO 02/36782, WO 03/092360, WO 05/012515 and WO 07/024,782. Glyphosate-tolerant plants can also be obtained by selecting plants containing naturally-occurring mutations of the above-mentioned genes, as described in for example WO 01/024615 or WO 03/013226. Plants expressing EPSPS genes that confer glyphosate tolerance are described in e.g. U.S. patent application Ser. Nos. 11/517,991, 10/739,610, 12/139,408, 12/352,532, 11/312,866, 11/315,678, 12/421,292, 11/400,598, 11/651,752, 11/681,285, 11/605,824, 12/468,205, 11/760,570, 11/762,526, 11/769,327, 11/769,255, 11/943,801 or 12/362,774. Plants comprising other genes that confer glyphosate tolerance, such as decarboxylase genes, are described in e.g. U.S. patent application Ser. Nos. 11/588,811, 11/185,342, 12/364,724, 11/185,560 or 12/423,926.

Other herbicide resistant plants are for example plants that are made tolerant to herbicides inhibiting the enzyme glutamine synthase, such as bialaphos, phosphinothricin or glufosinate. Such plants can be obtained by expressing an enzyme detoxifying the herbicide or a mutant glutamine synthase enzyme that is resistant to inhibition, e.g. described in U.S. patent application Ser. No. 11/760,602. One such efficient detoxifying enzyme is an enzyme encoding a phosphinothricin acetyltransferase (such as the bar or pat protein from Streptomyces species). Plants expressing an exogenous phosphinothricin acetyltransferase are for example described in U.S. Pat. Nos. 5,561,236; 5,648,477; 5,646,024; 5,273,894; 5,637,489; 5,276,268; 5,739,082; 5,908,810 and 7,112,665.

Further herbicide-tolerant plants are also plants that are made tolerant to the herbicides inhibiting the enzyme hydroxyphenylpyruvatedioxygenase (HPPD). Hydroxyphenylpyruvatedioxygenases are enzymes that catalyze the reaction in which para-hydroxyphenylpyruvate (HPP) is transformed into homogentisate. Plants tolerant to HPPD-inhibitors can be transformed with a gene encoding a naturally-occurring resistant HPPD enzyme, or a gene encoding a mutated or chimeric HPPD enzyme as described in WO 96/38567, WO 99/24585, WO 99/24586, WO 2009/144079, WO 2002/046387, or U.S. Pat. No. 6,768,044. Tolerance to HPPD-inhibitors can also be obtained by transforming plants with genes encoding certain enzymes enabling the formation of homogentisate despite the inhibition of the native HPPD enzyme by the HPPD-inhibitor. Such plants and genes are described in WO 99/34008 and WO 02/36787. Tolerance of plants to HPPD inhibitors can also be improved by transforming plants with a gene encoding an enzyme having prephenate deshydrogenase (PDH) activity in addition to a gene encoding an HPPD-tolerant enzyme, as described in WO 2004/024928. Further, plants can be made more tolerant to HPPD-inhibitor herbicides by adding into their genome a gene encoding an enzyme capable of metabolizing or degrading HPPD inhibitors, such as the CYP450 enzymes shown in WO 2007/103567 and WO 2008/150473.

Still further herbicide resistant plants are plants that are made tolerant to acetolactate synthase (ALS) inhibitors. Known ALS-inhibitors include, for example, sulfonylurea, imidazolinone, triazolopyrimidines, pryimidinyoxy(thio)benzoates, and/or sulfonylaminocarbonyltriazolinone herbicides. Different mutations in the ALS enzyme (also known as acetohydroxyacid synthase, AHAS) are known to confer tolerance to different herbicides and groups of herbicides, as described for example in Tranel and Wright (2002, Weed Science 50:700-712), but also, in U.S. Pat. Nos. 5,605,011, 5,378,824, 5,141,870, and 5,013,659. The production of sulfonylurea-tolerant plants and imidazolinone-tolerant plants is described in U.S. Pat. Nos. 5,605,011; 5,013,659; 5,141,870; 5,767,361; 5,731,180; 5,304,732; 4,761,373; 5,331,107; 5,928,937; and 5,378,824; and international publication WO 96/33270. Other imidazolinone-tolerant to plants are also described in for example WO 2004/040012, WO 2004/106529, WO 2005/020673, WO 2005/093093, WO 2006/007373, WO 2006/015376, WO 2006/024351, and WO 2006/060634. Further sulfonylurea- and imidazolinone-tolerant plants are also described in for example WO 07/024,782 and U.S. Patent Application No. 61/288,958.

Other plants tolerant to imidazolinone and/or sulfonylurea can be obtained by induced mutagenesis, selection in cell cultures in the presence of the herbicide or mutation breeding as described for example for soybeans in U.S. Pat. No. 5,084,082, for rice in WO 97/41218, for sugar beet in U.S. Pat. No. 5,773,702 and WO 99/057965, for lettuce in U.S. Pat. No. 5,198,599, or for sunflower in WO 01/065922.

Plants or plant cultivars (obtained by plant biotechnology methods such as genetic engineering) which may also be treated according to the invention are insect-resistant transgenic plants, i.e. plants made resistant to attack by certain target insects. Such plants can be obtained by genetic transformation, or by selection of plants containing a mutation imparting such insect resistance.

An “insect-resistant transgenic plant”, as used herein, includes any plant containing at least one transgene comprising a coding sequence encoding:

-   -   1) an insecticidal crystal protein from Bacillus thuringiensis         or an insecticidal portion thereof, such as the insecticidal         crystal proteins listed by Crickmore et al. (1998, Microbiology         and Molecular Biology Reviews, 62: 807-813), updated by         Crickmore et al. (2005) at the Bacillus thuringiensis toxin         nomenclature, online at:         http://www.lifesci.sussex.ac.uk/Home/Neil_Crickmore/Bt/), or         insecticidal portions thereof, e.g., proteins of the Cry protein         classes CrylAb, CrylAc, CryIB, CrylC, CrylD, Cry1F, Cry2Ab,         Cry3Aa, or Cry3Bb or insecticidal portions thereof (e.g. EP         1999141 and WO 2007/107302), or such proteins encoded by         synthetic genes as e.g. described in and U.S. patent application         Ser. No. 12/249,016; or     -   2) a crystal protein from Bacillus thuringiensis or a portion         thereof which is insecticidal in the presence of a second other         crystal protein from Bacillus thuringiensis or a portion         thereof, such as the binary toxin made up of the Cry34 and Cry35         crystal proteins (Moellenbeck et al. 2001, Nat. Biotechnol. 19:         668-72; Schnepf et al. 2006, Applied Environm. Microbiol. 71,         1765-1774) or the binary toxin made up of the Cry1A or Cry1F         proteins and the Cry2Aa or Cry2Ab or Cry2Ae proteins (U.S.         patent application Ser. No. 12/214,022 and EP 08010791.5); or     -   3) a hybrid insecticidal protein comprising parts of different         insecticidal crystal proteins from Bacillus thuringiensis, such         as a hybrid of the proteins of 1) above or a hybrid of the         proteins of 2) above, e.g., the Cry1A.105 protein produced by         corn event MON89034 (WO 2007/027777); or     -   4) a protein of any one of 1) to 3) above wherein some,         particularly 1 to 10, amino acids have been replaced by another         amino acid to obtain a higher insecticidal activity to a target         insect species, and/or to expand the range of target insect         species affected, and/or because of changes introduced into the         encoding DNA during cloning or transformation, such as the         Cry3Bb1 protein in corn events MON863 or MON88017, or the Cry3A         protein in corn event MIR604; or     -   5) an insecticidal secreted protein from Bacillus thuringiensis         or Bacillus cereus, or an insecticidal portion thereof, such as         the vegetative insecticidal (VIP) proteins listed at:         http://www.lifesci.sussex.ac.uk/home/Neil_Crickmore/Bt/vip.html,         e.g., proteins from the VIP3Aa protein class; or     -   6) a secreted protein from Bacillus thuringiensis or Bacillus         cereus which is insecticidal in the presence of a second         secreted protein from Bacillus thuringiensis or B. cereus, such         as the binary toxin made up of the VIP1A and VIP2A proteins (WO         94/21795); or     -   7) a hybrid insecticidal protein comprising parts from different         secreted proteins from Bacillus thuringiensis or Bacillus         cereus, such as a hybrid of the proteins in 1) above or a hybrid         of the proteins in 2) above; or     -   8) a protein of any one of 5) to 7) above wherein some,         particularly 1 to 10, amino acids have been replaced by another         amino acid to obtain a higher insecticidal activity to a target         insect species, and/or to expand the range of target insect         species affected, and/or because of changes introduced into the         encoding DNA during cloning or transformation (while still         encoding an insecticidal protein), such as the VIP3Aa protein in         cotton event COT 102; or     -   9) a secreted protein from Bacillus thuringiensis or Bacillus         cereus which is insecticidal in the presence of a crystal         protein from Bacillus thuringiensis, such as the binary toxin         made up of VIP3 and Cry1A or Cry1F (U.S. Patent Appl. No.         61/126,083 and 61/195,019), or the binary toxin made up of the         VIP3 protein and the Cry2Aa or Cry2Ab or Cry2Ae proteins (U.S.         patent application Ser. No. 12/214,022 and EP 08010791.5).     -   10) a protein of 9) above wherein some, particularly 1 to 10,         amino acids have been replaced by another amino acid to obtain a         higher insecticidal activity to a target insect species, and/or         to expand the range of target insect species affected, and/or         because of changes introduced into the encoding DNA during         cloning or transformation (while still encoding an insecticidal         protein)

Of course, an insect-resistant transgenic plant, as used herein, also includes any plant comprising a combination of genes encoding the proteins of any one of the above classes 1 to 10. In one embodiment, an insect-resistant plant contains more than one transgene encoding a protein of any one of the above classes 1 to 10, to expand the range of target insect species affected when using different proteins directed at different target insect species, or to delay insect resistance development to the plants by using different proteins insecticidal to the same target insect species but having a different mode of action, such as binding to different receptor binding sites in the insect.

An “insect-resistant transgenic plant”, as used herein, further includes any plant containing at least one transgene comprising a sequence producing upon expression a double-stranded RNA which upon ingestion by a plant insect pest inhibits the growth of this insect pest, as described e.g. in WO 2007/080126, WO 2006/129204, WO 2007/074405, WO 2007/080127 and WO 2007/035650.

Plants or plant cultivars (obtained by plant biotechnology methods such as genetic engineering) which may also be treated according to the invention are tolerant to abiotic stresses. Such plants can be obtained by genetic transformation, or by selection of plants containing a mutation imparting such stress resistance. Particularly useful stress tolerance plants include:

-   -   1) plants which contain a transgene capable of reducing the         expression and/or the activity of poly(ADP-ribose) polymerase         (PARP) gene in the plant cells or plants as described in WO         00/04173, WO/2006/045633, EP 04077984.5, or EP 06009836.5.     -   2) plants which contain a stress tolerance enhancing transgene         capable of reducing the expression and/or the activity of the         PARG encoding genes of the plants or plants cells, as described         e.g. in WO 2004/090140.     -   3) plants which contain a stress tolerance enhancing transgene         coding for a plant-functional enzyme of the nicotineamide         adenine dinucleotide salvage synthesis pathway including         nicotinamidase, nicotinate phosphoribosyltransferase, nicotinic         acid mononucleotide adenyl transferase, nicotinamide adenine         dinucleotide synthetase or nicotine amide         phosphorybosyltransferase as described e.g. in EP 04077624.7, WO         2006/133827, PCT/EP07/002,433, EP 1999263, or WO 2007/107326.

Plants or plant cultivars (obtained by plant biotechnology methods such as genetic engineering) which may also be treated according to the invention show altered quantity, quality and/or storage-stability of the harvested product and/or altered properties of specific ingredients of the harvested product such as:

-   -   1) transgenic plants which synthesize a modified starch, which         in its physical-chemical characteristics, in particular the         amylose content or the amylose/amylopectin ratio, the degree of         branching, the average chain length, the side chain         distribution, the viscosity behaviour, the gelling strength, the         starch grain size and/or the starch grain morphology, is changed         in comparison with the synthesised starch in wild type plant         cells or plants, so that this is better suited for special         applications. Said transgenic plants synthesizing a modified         starch are disclosed, for example, in EP 0571427, WO 95/04826,         EP 0719338, WO 96/15248, WO 96/19581, WO 96/27674, WO 97/11188,         WO 97/26362, WO 97/32985, WO 97/42328, WO 97/44472, WO 97/45545,         WO 98/27212, WO 98/40503, WO99/58688, WO 99/58690, WO 99/58654,         WO 00/08184, WO 00/08185, WO 00/08175, WO 00/28052, WO 00/77229,         WO 01/12782, WO 01/12826, WO 02/101059, WO 03/071860, WO         2004/056999, WO 2005/030942, WO 2005/030941, WO 2005/095632, WO         2005/095617, WO 2005/095619, WO 2005/095618, WO 2005/123927, WO         2006/018319, WO 2006/103107, WO 2006/108702, WO 2007/009823, WO         00/22140, WO 2006/063862, WO 2006/072603, WO 02/034923, EP         06090134.5, EP 06090228.5, EP 06090227.7, EP 07090007.1, EP         07090009.7, WO 01/14569, WO 02/79410, WO 03/33540, WO         2004/078983, WO 01/19975, WO 95/26407, WO 96/34968, WO 98/20145,         WO 99/12950, WO 99/66050, WO 99/53072, U.S. Pat. No. 6,734,341,         WO 00/11192, WO 98/22604, WO 98/32326, WO 01/98509, WO 01/98509,         WO 2005/002359, U.S. Pat. No. 5,824,790, U.S. Pat. No.         6,013,861, WO 94/04693, WO 94/09144, WO 94/11520, WO 95/35026,         WO 97/20936     -   2) transgenic plants which synthesize non starch carbohydrate         polymers or which synthesize non starch carbohydrate polymers         with altered properties in comparison to wild type plants         without genetic modification. Examples are plants producing         polyfructose, especially of the inulin and levan-type, as         disclosed in EP 0663956, WO 96/01904, WO 96/21023, WO 98/39460,         and WO 99/24593, plants producing alpha-1,4-glucans as disclosed         in WO 95/31553, US 2002031826, U.S. Pat. No. 6,284,479, U.S.         Pat. No. 5,712,107, WO 97/47806, WO 97/47807, WO 97/47808 and WO         00/14249, plants producing alpha-1,6 branched alpha-1,4-glucans,         as disclosed in WO 00/73422, plants producing alternan, as         disclosed in e.g. WO 00/47727, WO 00/73422, EP 06077301.7, U.S.         Pat. No. 5,908,975 and EP 0728213,     -   3) transgenic plants which produce hyaluronan, as for example         disclosed in WO 2006/032538, WO 2007/039314, WO 2007/039315, WO         2007/039316, JP 2006304779, and WO 2005/012529.     -   4) transgenic plants or hybrid plants, such as onions with         characteristics such as ‘high soluble solids content’, ‘low         pungency’ (LP) and/or ‘long storage’ (LS), as described in U.S.         patent application Ser. No. 12/020,360 and 61/054,026.

Plants or plant cultivars (that can be obtained by plant biotechnology methods such as genetic engineering) which may also be treated according to the invention are plants, such as cotton plants, with altered fiber characteristics. Such plants can be obtained by genetic transformation, or by selection of plants contain a mutation imparting such altered fiber characteristics and include:

-   -   a) Plants, such as cotton plants, containing an altered form of         cellulose synthase genes as described in WO 98/00549     -   b) Plants, such as cotton plants, containing an altered form of         rsw2 or rsw3 homologous nucleic acids as described in WO         2004/053219     -   c) Plants, such as cotton plants, with increased expression of         sucrose phosphate synthase as described in WO 01/17333     -   d) Plants, such as cotton plants, with increased expression of         sucrose synthase as described in WO 02/45485     -   e) Plants, such as cotton plants, wherein the timing of the         plasmodesmatal gating at the basis of the fiber cell is altered,         e.g. through downregulation of fiber-selective (3-1,3-glucanase         as described in WO 2005/017157, or as described in EP 08075514.3         or U.S. Patent Appl. No. 61/128,938     -   f) Plants, such as cotton plants, having fibers with altered         reactivity, e.g. through the expression of         N-acetylglucosaminetransferase gene including nodC and chitin         synthase genes as described in WO 2006/136351

Plants or plant cultivars (that can be obtained by plant biotechnology methods such as genetic engineering) which may also be treated according to the invention are plants, such as oilseed rape or related Brassica plants, with altered oil profile characteristics. Such plants can be obtained by genetic transformation, or by selection of plants contain a mutation imparting such altered oil profile characteristics and include:

-   -   a) Plants, such as oilseed rape plants, producing oil having a         high oleic acid content as described e.g. in U.S. Pat. No.         5,969,169, U.S. Pat. No. 5,840,946 or U.S. Pat. No. 6,323,392 or         U.S. Pat. No. 6,063,947     -   b) Plants such as oilseed rape plants, producing oil having a         low linolenic acid content as described in U.S. Pat. No.         6,270,828, U.S. Pat. No. 6,169,190, or U.S. Pat. No. 5,965,755     -   c) Plant such as oilseed rape plants, producing oil having a low         level of saturated fatty acids as described e.g. in U.S. Pat.         No. 5,434,283 or U.S. patent application Ser. No. 12/668,303

Plants or plant cultivars (that can be obtained by plant biotechnology methods such as genetic engineering) which may also be treated according to the invention are plants, such as oilseed rape or related Brassica plants, with altered seed shattering characteristics. Such plants can be obtained by genetic transformation, or by selection of plants contain a mutation imparting such altered seed shattering characteristics and include plants such as oilseed rape plants with delayed or reduced seed shattering as described in U.S. Patent Appl. No. 61/135,230 WO09/068,313 and WO10/006,732.

Particularly useful transgenic plants which may be treated according to the invention are plants containing transformation events, or combination of transformation events, that are the subject of petitions for non-regulated status, in the United States of America, to the Animal and Plant Health Inspection Service (APHIS) of the United States Department of Agriculture (USDA) whether such petitions are granted or are still pending. At any time this information is readily available from APHIS (4700 River Road Riverdale, Md. 20737, USA), for instance on its internet site (URL http://www.aphis.usda.gov/brs/not_reg.html). On the filing date of this application the petitions for nonregulated status that were pending with APHIS or granted by APHIS were those listed in table B which contains the following information:

-   -   Petition: the identification number of the petition. Technical         descriptions of the transformation events can be found in the         individual petition documents which are obtainable from APHIS,         for example on the APHIS website, by reference to this petition         number. These descriptions are herein incorporated by reference.     -   Extension of Petition: reference to a previous petition for         which an extension is requested.     -   Institution: the name of the entity submitting the petition.     -   Regulated article: the plant species concerned.     -   Transgenic phenotype: the trait conferred to the plants by the         transformation event.     -   Transformation event or line: the name of the event or events         (sometimes also designated as lines or lines) for which         nonregulated status is requested.     -   APHIS documents: various documents published by APHIS in         relation to the Petition and which can be requested with APHIS.

Additional particularly useful plants containing single transformation events or combinations of transformation events are listed for example in the databases from various national or regional regulatory agencies (see for example http://gmoinfo.jrc.it/gmp_browse.aspx and http://www.agbios.com/dbase.php).

Further particularly transgenic plants include plants containing a transgene in an agronomically neutral or beneficial position as described in any of the patent publications listed in Table C.

TABLE A Trait Reference Water use efficiency WO 2000/073475 Nitrogen use efficiency WO 1995/009911 WO 2007/076115 WO 1997/030163 WO 2005/103270 WO 2007/092704 WO 2002/002776 Improved photosynthesis WO 2008/056915 WO 2004/101751 Nematode resistance WO 1995/020669 WO 2003/033651 WO 2001/051627 WO 1999/060141 WO 2008/139334 WO 1998/012335 WO 2008/095972 WO 1996/030517 WO 2006/085966 WO 1993/018170 Reduced pod dehiscence WO 2006/009649 WO 1997/013865 WO 2004/113542 WO 1996/030529 WO 1999/015680 WO 1994/023043 WO 1999/000502 Aphid resistance WO 2006/125065 WO 2008/067043 WO 1997/046080 WO 2004/072109 Sclerotinia resistance WO 2006/135717 WO 2005/000007 WO 2006/055851 WO 2002/099385 WO 2005/090578 WO 2002/061043 Botrytis resistance WO 2006/046861 WO 2002/085105 Bremia resistance US 20070022496 WO 2004/049786 WO 2000/063432 Erwinia resistance WO 2004/049786 Closterovirus resistance WO 2007/073167 WO 2002/022836 WO 2007/053015 Stress tolerance (including WO 2010/019838 WO2008/002480 drought tolerance) WO 2009/049110 WO2005/033318 Tobamovirus resistance WO 2006/038794

TABLE B Petitions of Nonregulated Status Granted or Pending by APHIS as of Mar. 31, 2010 Applicant Documents Extension of Petition Regulated Transgenic Transformation Petition Number *** Institution Article Phenotype Event or Line Petitions for Nonregulated Status Pending 10-070-01p Virginia Tech Peanut Sclerotinia blight N70, P39, and resistant W171 09-349-01p Dow Soybean Herbicide Tolerant DAS-68416-4 AgroSciences 09-328-01p Bayer Crop Soybean Herbicide Tolerant FG72 Science 09-233-01p Dow Corn Herbicide Tolerant DAS-40278-9 09-201-01p Monsanto Soybean MON-877Ø5-6 09-183-01p Monsanto Soybean MON-87769 09-082-01p Monsanto Soybean Lepidopteran resistant MON 87701 09-063-01p Stine Seed Corn Glyphosate tolerant HCEM485 09-055-01p Monsanto Corn Drought Tolerant MON 87460 09-015-01p BASF Plant Soybean Herbicide Tolerant BPS-CV127-9 Science, LLC Soybean 08-366-01p ArborGen Eucalyptus Freeze Tolerant, ARB-FTE1-08 Fertility Altered 08-340-01p Bayer Cotton Glufosinate Tolerant, T304-40XGHB119 Insect Resistant 08-338-01p Pioneer Corn Male Sterile, Fertility DP-32138-1 Restored, Visual Marker 08-315-01p Florigene Rose Altered Flower Color IFD-524Ø1-4 and IFD-529Ø1-9 07-253-01p Syngenta Corn Lepidopteran resistant MIR-162 Maize 07-108-01p Syngenta Cotton Lepidopteran Resistant COT67B 06-354-01p Pioneer Soybean High Oleic Acid DP-3Ø5423-1 05-280-01p Syngenta Corn Thermostable alpha- 3272 amylase 04-110-01p Monsanto & Alfalfa Glyphosate Tolerant J101, J163 Forage Genetics 03-104-01p Monsanto & Creeping Glyphosate Tolerant ASR368 Scotts bentgrass Petitions for Nonregulated Status Granted 07-152-01p Pioneer Corn glyphosate & DP-098140-6 Imidazolinone tolerant 04-337-01p University of Papaya Papaya Ringspot Virus X17-2 Florida Resistant 06-332-01p Bayer Cotton Glyphosate tolerant GHB614 CropScience 06-298-01p Monsanto Corn European Corn Borer MON 89034 resistant 06-271-01p Pioneer Soybean Glyphosate & 356043 acetolactate synthase (DP-356Ø43-5) tolerant 06-234-01p 98-329-01p Bayer Rice Phosphinothricin LLRICE601 CropScience tolerant 06-178-01p Monsanto Soybean Glyphosate tolerant MON 89788 04-362-01p Syngenta Corn Corn Rootworm MIR604 Protected 04-264-01p ARS Plum Plum Pox Virus C5 Resistant 04-229-01p Monsanto Corn High Lysine LY038 04-125-01p Monsanto Corn Corn Rootworm 88017 Resistant 04-086-01p Monsanto Cotton Glyphosate Tolerant MON 88913 03-353-01p Dow Corn Corn Rootworm 59122 Resistant 03-323-01p Monsanto Sugar Glyphosate Tolerant H7-1 Beet 03-181-01p 00-136-01p Dow Corn Lepidopteran Resistant TC-6275 & Phosphinothricin tolerant 03-155-01p Syngenta Cotton Lepidopteran Resistant COT 102 03-036-01p Mycogen/Dow Cotton Lepidopteran Resistant 281-24-236 03-036-02p Mycogen/Dow Cotton Lepidopteran Resistant 3006-210-23 02-042-01p Aventis Cotton Phosphinothericin LLCotton25 tolerant 01-324-01p 98-216-01p Monsanto Rapeseed Glyphosate tolerant RT200 01-206-01p 98-278-01p Aventis Rapeseed Phosphinothricin MS1 & RF1/RF2 tolerant & pollination control 01-206-02p 97-205-01p Aventis Rapeseed Phosphinothricin Topas 19/2 tolerant 01-137-01p Monsanto Corn Corn Rootworm MON 863 Resistant 01-121-01p Vector Tobacco Reduced nicotine Vector 21-41 00-342-01p Monsanto Cotton Lepidopteran resistant Cotton Event 15985 00-136-01p Mycogen c/o Corn Lepidopteran resistant Line 1507 Dow & Pioneer phosphinothricin tolerant 00-011-01p 97-099-01p Monsanto Corn Glyphosate tolerant NK603 99-173-01p 97-204-01p Monsanto Potato PLRV & CPB resistant RBMT22-82 98-349-01p 95-228-01p AgrEvo Corn Phosphinothricin MS6 tolerant and Male sterile 98-335-01p U. of Flax Tolerant to soil CDC Triffid Saskatchewan residues of sulfonyl urea herbicide 98-329-01p AgrEvo Rice Phosphinothricin LLRICE06, tolerant LLRICE62 98-278-01p AgrEvo Rapeseed Phosphinothricin MS8 & RF3 tolerant & Pollination control 98-238-01p AgrEvo Soybean Phosphinothricin GU262 tolerant 98-216-01p Monsanto Rapeseed Glyphosate tolerant RT73 98-173-01p Novartis Seeds & Beet Glyphosate tolerant GTSB77 Monsanto 98-014-01p 96-068-01p AgrEvo Soybean Phosphinothricin A5547-127 tolerant 97-342-01p Pioneer Corn Male sterile & 676, 678, 680 Phosphinothricin tolerant 97-339-01p Monsanto Potato CPB & PVY resistant RBMT15-101, SEMT15-02, SEMT15-15 97-336-01p AgrEvo Beet Phosphinothricin T-120-7 tolerant 97-287-01p Monsanto Tomato Lepidopteran resistant 5345 97-265-01p AgrEvo Corn Phosphinothricin CBH-351 tolerant & Lep. resistant 97-205-01p AgrEvo Rapeseed Phosphinothricin T45 tolerant 97-204-01p Monsanto Potato CPB & PLRV resistant RBMT21-129 & RBMT21-350 97-148-01p Bejo Cichorium Male sterile RM3-3, RM3-4, intybus RM3-6 97-099-01p Monsanto Corn Glyphosate tolerant GA21 97-013-01p Calgene Cotton Bromoxynil tolerant & Events 31807 & Lepidopteran resistant 31808 97-008-01p Du Pont Soybean Oil profile altered G94-1, G94-19, G- 168 96-317-01p Monsanto Corn Glyphosate tolerant & MON802 ECB resistant 96-291-01p DeKalb Corn European Corn Borer DBT418 resistant 96-248-01p 92-196-01p Calgene Tomato Fruit ripening altered 1 additional FLAVRSAVR line 96-068-01p AgrEvo Soybean Phosphinothricin W62, W98, A2704- tolerant 12, A2704-21, A5547-35 96-051-01p Cornell U Papaya PRSV resistant 55-1, 63-1 96-017-01p 95-093-01p Monsanto Corn European Corn Borer MON809 & resistant MON810 95-352-01p Asgrow Squash CMV, ZYMV, WMV2 CZW-3 resistant 95-338-01p Monsanto Potato CPB resistant SBT02-5 & -7, ATBT04-6 &-27, -30, -31, -36 95-324-01p Agritope Tomato Fruit ripening altered 35 1 N 95-256-01p Du Pont Cotton Sulfonylurea tolerant 19-51a 95-228-01p Plant Genetic Corn Male sterile MS3 Systems 95-195-01p Northrup King Corn European Corn Borer Bt11 resistant 95-179-01p 92-196-01p Calgene Tomato Fruit ripening altered 2 additional FLAVRSAVR lines 95-145-01p DeKalb Corn Phosphinothricin B16 tolerant 95-093-01p Monsanto Corn Lepidopteran resistant MON 80100 95-053-01p Monsanto Tomato Fruit ripening altered 8338 95-045-01p Monsanto Cotton Glyphosate tolerant 1445, 1698 95-030-01p 92-196-01p Calgene Tomato Fruit ripening altered 20 additional FLAVRSAVR lines 94-357-01p AgrEvo Corn Phosphinothricin T14, T25 tolerant 94-319-01p Ciba Seeds Corn Lepidopteran resistant Event 176 94-308-01p Monsanto Cotton Lepidopteran resistant 531, 757, 1076 94-290-01p Zeneca & Tomato Fruit polygalacturonase B, Da, F Petoseed level decreased 94-257-01p Monsanto Potato Coleopteran resistant BT6, BT10, BT12, BT16, BT17, BT18, BT23 94-230-01p 92-196-01p Calgene Tomato Fruit ripening altered 9 additional FLAVRSAVR lines 94-228-01p DNA Plant Tech Tomato Fruit ripening altered 1345-4 94-227-01p 92-196-01p Calgene Tomato Fruit ripening altered Line N73 1436-111 94-090-01p Calgene Rapeseed Oil profile altered pCGN3828- 212/86- 18 & 23 93-258-01p Monsanto Soybean Glyphosate tolerant 40-3-2 93-196-01p Calgene Cotton Bromoxynil tolerant BXN 92-204-01p Upjohn Squash WMV2 & ZYMV ZW-20 resistant 92-196-01p Calgene Tomato Fruit ripening altered FLAVR SAVR NOTE: To obtain the most up-to-date list of Crops No Longer Regulated, please look at the Current Status of Petitions. This list is automatically updated and reflects all petitions received to date by APHIS, including petitions pending, withdrawn, or approved. Abbreviations: CMV—cucumber mosaic virus; CPB—colorado potato beetle; PLRV—potato leafroll virus; PRSV—papaya ringspot virus; PVY—potato virus Y; WMV2—watermelon mosaic virus 2 ZYMV—zucchini yellow mosaic virus *** Extension of Petition Number: Under 7CFR 340.6(e) a person may request that APHIS extend a determination of non-regulated status to other organisms based on their similarity of the previously deregulated article. This column lists the previously granted petition of that degregulated article. **** Preliminary EA: The Environmental Assessment initially available for Public comment prior to finalization.

TABLE C Plant species Event Trait Patent reference Corn PV-ZMGT32 (NK603) Glyphosate tolerance US 2007-056056 Corn MIR604 Insect resistance (Cry3a055) EP 1 737 290 Corn LY038 High lysine content U.S. Pat. No. 7,157,281 Corn 3272 Self processing corn (alpha- US 2006-230473 amylase) Corn PV-ZMIR13 Insect resistance (Cry3Bb) US 2006-095986 (MON863) Corn DAS-59122-7 Insect resistance US 2006-070139 (Cry34Ab1/Cry35Ab1) Corn TC1507 Insect resistance (Cry1F) U.S. Pat. No. 7,435,807 Corn MON810 Insect resistance (Cry1Ab) US 2004-180373 Corn VIP1034 Insect resistance WO 03/052073 Corn B16 Glufosinate resistance US 2003-126634 Corn GA21 Glyphosate resistance U.S. Pat. No. 6,040,497 Corn GG25 Glyphosate resistance U.S. Pat. No. 6,040,497 Corn GJ11 Glyphosate resistance U.S. Pat. No. 6,040,497 Corn FI117 Glyphosate resistance U.S. Pat. No. 6,040,497 Corn GAT-ZM1 Glufosinate tolerance WO 01/51654 Corn MON87460 Drought tolerance WO 2009/111263 Corn DP-098140-6 Glyphosate tolerance/ALS WO 2008/112019 inhibitor tolerance Wheat Event 1 Fusarium resistance CA 2561992 (trichothecene 3-O- acetyltransferase) Sugar beet T227-1 Glyphosate tolerance US 2004-117870 Sugar beet H7-1 Glyphosate tolerance WO 2004-074492 Soybean MON89788 Glyphosate tolerance US 2006-282915 Soybean A2704-12 Glufosinate tolerance WO 2006/108674 Soybean A5547-35 Glufosinate tolerance WO 2006/108675 Soybean DP-305423-1 High oleic acid/ALS inhibitor WO 2008/054747 tolerance Rice GAT-OS2 Glufosinate tolerance WO 01/83818 Rice GAT-OS3 Glufosinate tolerance US 2008-289060 Rice PE-7 Insect resistance (Cry1Ac) WO 2008/114282 Oilseed rape MS-B2 Male sterility WO 01/31042 Oilseed rape MS-BN1/RF-BN1 Male sterility/restoration WO 01/41558 Oilseed rape RT73 Glyphosate resistance WO 02/36831 Cotton CE43-67B Insect resistance (Cry1Ab) WO 2006/128573 Cotton CE46-02A Insect resistance (Cry1Ab) WO 2006/128572 Cotton CE44-69D Insect resistance (Cry1Ab) WO 2006/128571 Cotton 1143-14A Insect resistance (Cry1Ab) WO 2006/128569 Cotton 1143-51B Insect resistance (Cry1Ab) WO 2006/128570 Cotton T342-142 Insect resistance (Cry1Ab) WO 2006/128568 Cotton event3006-210-23 Insect resistance (Cry1Ac) WO 2005/103266 Cotton PV-GHGT07 (1445) Glyphosate tolerance US 2004-148666 Cotton MON88913 Glyphosate tolerance WO 2004/072235 Cotton EE-GH3 Glyphosate tolerance WO 2007/017186 Cotton T304-40 Insect-resistance (Cry1Ab) WO2008/122406 Cotton Cot202 Insect resistance (VIP3) US 2007-067868 Cotton LLcotton25 Glufosinate resistance WO 2007/017186 Cotton EE-GH5 Insect resistance (Cry1Ab) WO 2008/122406 Cotton event 281-24-236 Insect resistance (Cry1F) WO 2005/103266 Cotton Cot102 Insect resistance (Vip3A) US 2006-130175 Cotton MON 15985 Insect resistance (Cry1A/Cry2Ab) US 2004-250317 Bent Grass Asr-368 Glyphosate tolerance US 2006-162007 Brinjal EE-1 Insect resistance (Cry1Ac) WO 2007/091277

Among the diseases of plants or crops that can be controlled by the method according to the invention, mention can be made of:

Powdery mildew diseases such as:

-   -   Blumeria diseases, caused for example by Blumeria graminis;     -   Podosphaera diseases, caused for example by Podosphaera         leucotricha;     -   Sphaerotheca diseases, caused for example by Sphaerotheca         fuliginea;     -   Uncinula diseases, caused for example by Uncinula necator;         Rust diseases such as:     -   Gymnosporangium diseases, caused for example by Gymnosporangium         sabinae;     -   Hemileia diseases, caused for example by Hemileia vastatrix;     -   Phakopsora diseases, caused for example by Phakopsora pachyrhizi         or Phakopsora meibomiae;     -   Puccinia diseases, caused for example by Puccinia recondite,         Puccinia graminis or Puccinia striiformis;     -   Uromyces diseases, caused for example by Uromyces         appendiculatus;         Oomycete diseases such as:     -   Albugo diseases caused for example by Albugo candida;     -   Bremia diseases, caused for example by Bremia lactucae;     -   Peronospora diseases, caused for example by Peronospora pisi         or P. brassicae;     -   Phytophthora diseases, caused for example by Phytophthora         infestans;     -   Plasmopara diseases, caused for example by Plasmopara viticola;     -   Pseudoperonospora diseases, caused for example by         Pseudoperonospora humuli or Pseudoperonospora cubensis;     -   Pythium diseases, caused for example by Pythium ultimum;         Leafspot, leaf blotch and leaf blight diseases such as:     -   Alternaria diseases, caused for example by Alternaria solani;     -   Cercospora diseases, caused for example by Cercospora beticola;     -   Cladiosporum diseases, caused for example by Cladiosporium         cucumerinum;     -   Cochliobolus diseases, caused for example by Cochliobolus         sativus (Conidiaform: Drechslera, Syn: Helminthosporium) or         Cochliobolus miyabeanus;     -   Colletotrichum diseases, caused for example by Colletotrichum         lindemuthanium;     -   Cycloconium diseases, caused for example by Cycloconium         oleaginum;     -   Diaporthe diseases, caused for example by Diaporthe citri;     -   Elsinoe diseases, caused for example by Elsinoe fawcettii;     -   Gloeosporium diseases, caused for example by Gloeosporium         laeticolor;     -   Glomerella diseases, caused for example by Glomerella cingulata;     -   Guignardia diseases, caused for example by Guignardia bidwelli;     -   Leptosphaeria diseases, caused for example by Leptosphaeria         maculans; Leptosphaeria nodorum;     -   Magnaporthe diseases, caused for example by Magnaporthe grisea;     -   Mycosphaerella diseases, caused for example by Mycosphaerella         graminicola; Mycosphaerella arachidicola; Mycosphaerella         fijiensis;     -   Phaeosphaeria diseases, caused for example by Phaeosphaeria         nodorum;     -   Pyrenophora diseases, caused for example by Pyrenophora teres,         or Pyrenophora tritici repentis;     -   Ramularia diseases, caused for example by Ramularia collo-cygni,         or Ramularia areola;     -   Rhynchosporium diseases, caused for example by Rhynchosporium         secalis;     -   Septoria diseases, caused for example by Septoria apii or         Septoria lycopercisi;     -   Typhula diseases, caused for example by Typhula incamata;     -   Venturia diseases, caused for example by Venturia inaequalis;         Root, Sheath and stem diseases such as:     -   Corticium diseases, caused for example by Corticium graminearum;     -   Fusarium diseases, caused for example by Fusarium oxysporum;     -   Gaeumannomyces diseases, caused for example by Gaeumannomyces         graminis;     -   Rhizoctonia diseases, caused for example by Rhizoctonia solani;     -   Sarocladium diseases caused for example by Sarocladium oryzae;     -   Sclerotium diseases caused for example by Sclerotium oryzae;     -   Tapesia diseases, caused for example by Tapesia acuformis;     -   Thielaviopsis diseases, caused for example by Thielaviopsis         basicola;         Ear and panicle diseases such as:     -   Alternaria diseases, caused for example by Alternaria spp.;     -   Aspergillus diseases, caused for example by Aspergillus flavus;     -   Cladosporium diseases, caused for example by Cladosporium spp.;     -   Claviceps diseases, caused for example by Claviceps purpurea;     -   Fusarium diseases, caused for example by Fusarium culmorum;     -   Gibberella diseases, caused for example by Gibberella zeae;     -   Monographella diseases, caused for example by Monographella         nivalis;         Smut and bunt diseases such as:     -   Sphacelotheca diseases, caused for example by Sphacelotheca         reiliana;     -   Tilletia diseases, caused for example by Tilletia caries;     -   Urocystis diseases, caused for example by Urocystis occulta;     -   Ustilago diseases, caused for example by Ustilago nuda;         Fruit rot and mould diseases such as:     -   Aspergillus diseases, caused for example by Aspergillus flavus;     -   Botrytis diseases, caused for example by Botrytis cinerea;     -   Penicillium diseases, caused for example by Penicillium         expansum;     -   Rhizopus diseases caused by example by Rhizopus stolonifer     -   Sclerotinia diseases, caused for example by Sclerotinia         sclerotiorum;     -   Verticilium diseases, caused for example by Verticilium         alboatrum;         Seed and soilborne decay, mould, wilt, rot and damping-off         diseases:     -   Alternaria diseases, caused for example by Alternaria         brassicicola     -   Aphanomyces diseases, caused for example by Aphanomyces         euteiches     -   Ascochyta diseases, caused for example by Ascochyta lentis     -   Aspergillus diseases, caused for example by Aspergillus flavus     -   Cladosporium diseases, caused for example by Cladosporium         herbarum     -   Cochliobolus diseases, caused for example by Cochliobolus         sativus (Conidiaform: Drechslera, Bipolaris Syn:         Helminthosporium);     -   Colletotrichum diseases, caused for example by Colletotrichum         coccodes;     -   Fusarium diseases, caused for example by Fusarium culmorum;     -   Gibberella diseases, caused for example by Gibberella zeae;     -   Macrophomina diseases, caused for example by Macrophomina         phaseolina     -   Monographella diseases, caused for example by Monographella         nivalis;     -   Penicillium diseases, caused for example by Penicillium expansum     -   Phoma diseases, caused for example by Phoma lingam     -   Phomopsis diseases, caused for example by Phomopsis sojae;     -   Phytophthora diseases, caused for example by Phytophthora         cactorum;     -   Pyrenophora diseases, caused for example by Pyrenophora graminea     -   Pyricularia diseases, caused for example by Pyricularia oryzae;     -   Pythium diseases, caused for example by Pythium ultimum;     -   Rhizoctonia diseases, caused for example by Rhizoctonia solani;     -   Rhizopus diseases, caused for example by Rhizopus oryzae     -   Sclerotium diseases, caused for example by Sclerotium rolfsii;     -   Septoria diseases, caused for example by Septoria nodorum;     -   Typhula diseases, caused for example by Typhula incarnate;     -   Verticillium diseases, caused for example by Verticillium         dahliae;         Canker, broom and dieback diseases such as:     -   Nectria diseases, caused for example by Nectria galligena;         Blight diseases such as:     -   Monilinia diseases, caused for example by Monilinia laxa;         Leaf blister or leaf curl diseases such as:     -   Exobasidium diseases caused for example by Exobasidium vexans     -   Taphrina diseases, caused for example by Taphrina deformans;         Decline diseases of wooden plants such as:     -   Esca diseases, caused for example by Phaemoniella clamydospora;     -   Eutypa dyeback, caused for example by Eutypa lata;     -   Ganoderma diseases caused for example by Ganoderma boninense;     -   Rigidoporus diseases caused for example by Rigidoporus lignosus         Diseases of Flowers and Seeds such as     -   Botrytis diseases caused for example by Botrytis cinerea;         Diseases of Tubers such as     -   Rhizoctonia diseases caused for example by Rhizoctonia solani;     -   Helminthosporium diseases caused for example by Helminthosporium         solani;         Club root diseases such as     -   Plasmodiophora diseases, cause for example by Plamodiophora         brassicae.         Diseases caused by Bacterial Organisms such as     -   Xanthomonas species for example Xanthomonas campestris pv.         oryzae;     -   Pseudomonas species for example Pseudomonas syringae pv.         lachrymans;     -   Erwinia species for example Erwinia amylovora.

The composition according to the invention may also be used against fungal diseases liable to grow on or inside timber. The term “timber” means all types of species of wood, and all types of working of this wood intended for construction, for example solid wood, high-density wood, laminated wood, and plywood. The method for treating timber according to the invention mainly consists in contacting one or more compounds according to the invention or a composition according to the invention; this includes for example direct application, spraying, dipping, injection or any other suitable means.

The dose of active compound usually applied in the method of treatment according to the invention is generally and advantageously from 10 to 800 g/ha, preferably from 50 to 300 g/ha for applications in foliar treatment. The dose of active substance applied is generally and advantageously from 2 to 200 g per 100 kg of seed, preferably from 3 to 150 g per 100 kg of seed in the case of seed treatment.

It is clearly understood that the doses indicated herein are given as illustrative examples of the method according to the invention. A person skilled in the art will know how to adapt the application doses, notably according to the nature of the plant or crop to be treated.

The compounds or mixtures according to the invention can also be used for the preparation of composition useful to curatively or preventively treat human or animal fungal diseases such as, for example, mycoses, dermatoses, trichophyton diseases and candidiases or diseases caused by Aspergillus spp., for example Aspergillus fumigatus.

The various aspects of the invention will now be illustrated with reference to the following table of compound examples and the following preparation or efficacy examples.

Table 1 illustrates in a non-limiting manner examples of compounds of formula (I) according to the invention:

In table 1, unless otherwise specified, M+H (Apcl+) means the molecular ion peak plus 1 a.m.u. (atomic mass unit) as observed in mass spectroscopy via positive atmospheric pressure chemical ionisation.

In table 1, the logP values were determined in accordance with EEC Directive 79/831 Annex V.A8 by HPLC (High Performance Liquid Chromatography) on a reversed-phase column (C 18), using the method described below:

Temperature: 40° C.; Mobile phases: 0.1% aqueous formic acid and acetonitrile; linear gradient from 10% acetonitrile to 90% acetonitrile.

Calibration was carried out using unbranched alkan-2-ones (comprising 3 to 16 carbon atoms) with known logP values (determination of the logP values by the retention times using linear interpolation between two successive alkanones). lambda-max-values were determined using UV-spectra from 200 nm to 400 nm and the peak values of the chromatographic signals.

TABLE 1 Mass Example X1 X2 Y T Z1 Z2 Z3 W B logP (M + H) 1 F F Me O cyclopentyl H H CH2 phenyl 3.69 366 2 F F Me O isopropyl H H CH2 phenyl 3.19 340 3 F F Me O 2-cyanoethyl H H CH2 phenyl 2.39 351 4 F F Me O methyl H H CH2 phenyl 2.43 312 5 F F Me O 2,2,2- H H CH2 phenyl 3.25 380 trifluoroethyl 6 Cl F Me O cyclopentyl H H CH2 phenyl 3.89 382 7 Cl F Me O isopropyl H H CH2 phenyl 3.35 356 8 Cl F Me O 2-cyanoethyl H H CH2 phenyl 2.53 367 9 Cl F Me O methyl H H CH2 phenyl 2.60 328 10 Cl F Me O 2,2,2- H H CH2 phenyl 3.39 396 trifluoroethyl 11 F F Me O cyclopropyl H H CH2 phenyl 2.88 338 12 Cl F Me O cyclopropyl H H CH2 phenyl 3.06 354 13 F F Me O cyclopropyl H H CH(Me) phenyl 3.17 352 14 Cl F Me O cyclopropyl H H CH(Me) phenyl 3.31 368 15 F F Me S cyclopropyl H H CH(Me) phenyl 3.92 368 16 Cl F Me S cyclopropyl H H CH(Me) phenyl 4.11 384 17 F F Me O ethyl Me H C═O phenyl 2.59 354 18 Cl F Me O ethyl Me H C═O phenyl 2.71 370 19 F F Me O cyclopropyl Me H CH2 2-fluorophenyl 3.37 370 20 Cl F Me O cyclopropyl Me H CH2 2-fluorophenyl 3.52 386 21 F F Me S cyclopropyl Me H CH2 2-fluorophenyl 4.01 386 22 F F Me O methyl H H CH2 4-fluorophenyl 2.50 330 23 F F Me O isopropyl H H CH2 4-fluorophenyl 3.23 358 24 Cl F Me O methyl H H CH2 4-fluorophenyl 2.66 346 25 Cl F Me O isopropyl H H CH2 4-fluorophenyl 3.37 374 26 F F Me O cyclopropyl Me H CH2 2,6-difluorophenyl 3.42 388 27 Cl F Me O cyclopropyl Me H CH2 2,6-difluorophenyl 3.57 404 28 F F Me S cyclopropyl Me H CH2 2,6-difluorophenyl 3.94 404 29 Cl F Me O H H H CH(Me) 2,6-difluorophenyl 2.92 364 30 F F Me O H H H CH(Me) 2,6-difluorophenyl 2.78 348 31 F F Me O H Me H CH2 2-chlorophenyl 2.94 346 32 F F Me O H H H CH2 2-chlorophenyl 2.69 332 33 Cl F Me O H Me H CH2 2-chlorophenyl 3.15 362 34 Cl F Me O H H H CH2 2-chlorophenyl 2.88 348 35 F F Me O methyl H H CH2 2-chlorophenyl 2.76 346 36 Cl F Me O methyl H H CH2 2-chlorophenyl 2.92 362 37 F F Me S H Me H CH2 2-chlorophenyl 3.61 362 38 Cl F Me S H Me H CH2 2-chlorophenyl 3.72 378 39 F F Me O H H H CH(Me) 2-chlorophenyl 2.94 346 40 Cl F Me O H H H CH(Me) 2-chlorophenyl 3.15 362 41 F F Me O cyclopropyl Me H CH(Me) 2-chlorophenyl 3.87 400 42 Cl F Me O cyclopropyl Me H CH(Me) 2-chlorophenyl 4.08 416 43 F F Me S cyclopropyl Me H CH(Me) 2-chlorophenyl 4.72 416 44 F F Me O cyclopropyl H H CF2 2-chlorophenyl 3.39 408 45 F F Me O H H H C(Me)2 2-chlorophenyl 3.27 360 46 Cl F Me O H H H C(Me)2 2-chlorophenyl 3.48 376 47 F F Me O H H H CH2 3-chlorophenyl 2.75 332 48 Cl F Me O H Me H CH2 3-chlorophenyl 3.17 362 49 Cl F Me O H H H CH2 3-chlorophenyl 2.92 348 50 F F Me O H Me H CH2 3-chlorophenyl 3.02 346 51 F F Me O H H H CH(Me) 3-chlorophenyl 3.02 346 52 Cl F Me O H H H CH(Me) 3-chlorophenyl 3.21 362 53 F F Me O H H H C(Me)2 3-chlorophenyl 3.31 360 54 Cl F Me O H H H C(Me)2 3-chlorophenyl 3.53 376 55 F F Me O cyclopropyl Me H CH2 4-chlorophenyl 3.73 386 56 F F Me O ethyl H H CH2 4-chlorophenyl 3.19 360 57 Cl F Me O ethyl H H CH2 4-chlorophenyl 3.35 376 58 F F Me S ethyl H H CH2 4-chlorophenyl 3.92 376 59 Cl F Me O H H H CH(iPr) 4-chlorophenyl 3.94 390 60 F F Me O H H H CH(iPr) 4-chlorophenyl 3.78 374 61 F F Me O methyl H H C═O 4-chlorophenyl 2.53 360 62 Cl F Me O methyl H H C═O 4-chlorophenyl 2.68 376 63 F F Me O H H H C(Me)2 4-chlorophenyl 3.37 360 64 Cl F Me O H H H C(Me)2 4-chlorophenyl 3.58 376 65 F F Me O H H H CH2 2,4-dichlorophenyl 3.09 66 Cl F Me O H H H CH2 2,4-dichlorophenyl 3.31 67 F F Me O H Me H CH2 2,4-dichlorophenyl 3.46 380 68 Cl F Me O H Me H CH2 2,4-dichlorophenyl 3.67 396 69 Cl F Me S H Me H CH2 2,4-dichlorophenyl 4.29 412 70 F F Me S H Me H CH2 2,4-dichlorophenyl 4.16 396 71 F F Me S H H H CH2 2,4-dichlorophenyl 3.99 382 72 Cl F Me S H H H CH2 2,4-dichlorophenyl 4.11 398 73 F F Me O H Me H CH(OMe) 2,4-dichlorophenyl 3.65 + 3.75⁽¹⁾ 410 74 Cl F Me O H H H CH(OMe) 2,4-dichlorophenyl 3.48 412 75 F F Me O H H H CH(OMe) 2,4-dichlorophenyl 3.25 396 76 Cl F Me O H Et H CH(OMe) 2,4-dichlorophenyl 4.18 + 4.23⁽¹⁾ 440 77 F F Me O H Et H CH(OMe) 2,4-dichlorophenyl 3.94 424 78 Cl F Me O H

CH(OMe) 2,4-dichlorophenyl 3.70 438 79 F F Me O H

CH(OMe) 2,4-dichlorophenyl 3.46 422 80 F F Me O cyclopropyl H H CH(OMe) 2,4-dichlorophenyl 436 81 F F Me O cyclopropyl Me H CH(OMe) 2,4-dichlorophenyl 450 82 Cl F Me O H Me H CH(OEt) 2,4-dichlorophenyl 4.37 + 4.46⁽¹⁾ 440 83 F F Me O H Me H CH(OEt) 2,4-dichlorophenyl 4.11 + 4.20⁽¹⁾ 424 84 F F Me O H H H CH(Me) 2,4-dichlorophenyl 3.46 380 85 Cl F Me O H H H CH(Me) 2,4-dichlorophenyl 3.67 396 86 F F Me O cyclopropyl H H CF2 2,4-dichlorophenyl 3.94 442 87 F F Me O H H H C(Me)2 2,4-dichlorophenyl 3.81 394 88 Cl F Me O H H H C(Me)2 2,4-dichlorophenyl 4.03 410 89 Cl F Me S H H H C(Me)2 2,4-dichlorophenyl 4.72 426 90 F F Me O H H H CH2 2,5-dichlorophenyl 3.11 366 91 Cl F Me O H H H CH2 2,5-dichlorophenyl 3.29 382 92 F F Me O H Me H CH2 2,5-dichlorophenyl 3.37 380 93 Cl F Me O H Me H CH2 2,5-dichlorophenyl 3.53 396 94 F F Me O methyl H H CH2 2,5-dichlorophenyl 3.17 380 95 Cl F Me O methyl H H CH2 2,5-dichlorophenyl 3.33 396 96 F F Me S methyl H H CH2 2,5-dichlorophenyl 3.87 396 97 F F Me O H H H CH(Me) 2,5-dichlorophenyl 3.35 380 98 Cl F Me O H H H CH(Me) 2,5-dichlorophenyl 3.55 396 99 F F Me O cyclopropyl H H CF2 2,5-dichlorophenyl 3.85 442 100 F F Me O H H H C(Me)2 2,5-dichlorophenyl 3.68 394 101 Cl F Me O H H H C(Me)2 2,5-dichlorophenyl 3.89 410 102 F F Me O H Me H CH2 3,5-dichlorophenyl 3.48 380 103 F F Me O H H H CH2 3,5-dichlorophenyl 3.25 366 104 Cl F Me O H Me H CH2 3,5-dichlorophenyl 3.67 396 105 Cl F Me O H H H CH2 3,5-dichlorophenyl 3.42 382 106 Cl F Me O H H H CH(OMe) 3,5-dichlorophenyl 3.55 412 107 F F Me O H H H CH(OMe) 3,5-dichlorophenyl 3.33 396 108 Cl F Me O H Me H CH(OMe) 3,5-dichlorophenyl 3.79 + 3.92⁽¹⁾ 426 109 F F Me O H Me H CH(OMe) 3,5-dichlorophenyl 3.55 + 3.70⁽¹⁾ 410 110 F F Me S H H H CH(OMe) 3,5-dichlorophenyl 4.19 412 111 F F Me O H H H CH(Me) 3,5-dichlorophenyl 3.55 380 112 Cl F Me O H H H CH(Me) 3,5-dichlorophenyl 3.73 396 113 F F Me O H H H C(Me)2 3,5-dichlorophenyl 3.87 394 114 Cl F Me O H H H C(Me)2 3,5-dichlorophenyl 4.01 410 115 F F Me O cyclopropyl Me H CH2 2,6-dichlorophenyl 4.06 420 116 Cl F Me O cyclopropyl Me H CH2 2,6-dichlorophenyl 4.29 436 117 F F Me O H H H CH2 2,6-dichlorophenyl 3.00 366 118 Cl F Me O H H H CH2 2,6-dichlorophenyl 3.21 382 119 Cl F Me O cyclopropyl Me H CH2 2-chloro-6-fluorophenyl 3.94 420 120 F F Me O cyclopropyl Me H CH2 2-chloro-6-fluorophenyl 3.76 404 121 F F Me O H H H CH2 2-(trifluoromethyl)phenyl 2.92 366 122 Cl F Me O H H H CH2 2-(trifluoromethyl)phenyl 3.11 382 123 F F Me O methyl H H CH2 2-(trifluoromethyl)phenyl 3.00 380 124 Cl F Me O methyl H H CH2 2-(trifluoromethyl)phenyl 3.13 396 125 Cl F Me O H H H CH(Me) 3-(trifluoromethyl)phenyl 3.35 396 126 F F Me O H H H CH(Me) 3-(trifluoromethyl)phenyl 3.23 380 127 F F Me O H H H CH(Me) 4-(trifluoromethyl)phenyl 3.25 380 128 Cl F Me O H H H CH(Me) 4-(trifluoromethyl)phenyl 3.39 396 129 F F Me O methyl H H CH2 3,4-dimethoxyphenyl 2.04 372 130 F F Me O cyclohexyl H H CH2 3,4-dimethoxyphenyl 3.42 440 131 Cl F Me O methyl H H CH2 3,4-dimethoxyphenyl 2.18 388 132 Cl F Me O cyclohexyl H H CH2 3,4-dimethoxyphenyl 3.53 456 133 F F Me O H Me Me C═O 4-bromo-2-methylphenyl 3.37 432 134 F F Me O isopropyl H H CH2 2,4,6-trimethylphenyl 4.30 382 135 F F Me O methyl H H CH2 2,4,6-trimethylphenyl 3.48 354 136 Cl F Me O isopropyl H H CH2 2,4,6-trimethylphenyl 4.49 398 137 Cl F Me O methyl H H CH2 2,4,6-trimethylphenyl 3.67 370 138 F F Me O methyl H H CH2 4-tert-butylphenyl 3.78 368 139 Cl F Me O methyl H H CH2 4-tert-butylphenyl 3.96 384 140 F F Me O H H H CH2 2-phenoxyphenyl 3.48 390 141 Cl F Me O H H H CH2 2-phenoxyphenyl 3.64 406 142 F F Me O H Me Me CH2 3-phenoxyphenyl 4.09 418 143 F F Me O H H H CH2 3-phenoxyphenyl 3.37 390 144 Cl F Me O H Me Me CH2 3-phenoxyphenyl 4.30 434 145 Cl F Me O H H H CH2 3-phenoxyphenyl 3.55 406 146 F F Me O H Me H CH2 3-phenoxyphenyl 3.64 404 147 Cl F Me O H Me H CH2 3-phenoxyphenyl 3.80 420 148 F F Me O H H H C(Me)2 3-phenoxyphenyl 3.92 418 149 Cl F Me O H H H C(Me)2 3-phenoxyphenyl 4.15 434 150 F F Me O H Me Me CH2 4-phenoxyphenyl 4.19 418 151 F F Me O H Me H CH2 4-phenoxyphenyl 3.63 404 152 F F Me O H H H CH2 4-phenoxyphenyl 3.41 390 153 Cl F Me O H Me Me CH2 4-phenoxyphenyl 4.39 434 154 Cl F Me O H Me H CH2 4-phenoxyphenyl 3.83 420 155 Cl F Me O H H H CH2 4-phenoxyphenyl 3.60 406 156 F F Me S H Me H CH2 4-phenoxyphenyl 4.29 420 157 F F Me O H H H C(Me)2 4-phenoxyphenyl 4.06 418 158 Cl F Me O H H H C(Me)2 4-phenoxyphenyl 4.21 434 159 Cl F Me O H Me H CH(OMe) 4-methoxy-3-(prop-2- 2.76 442 yn-1-yloxy)-phenyl 160 F F Me O H Me Me C═ O 2-naphthyl 2.92 390 161 F F Me O H H H CH(CF3) 2-thienyl 2.75 372 162 Cl F Me O H H H CH(CF3) 2-thienyl 2.92 388 163 Cl F Me O H H H CH2 3-methyl-2-thienyl 2.68 334 164 F F Me O H H H CH2 3-methyl-2-thienyl 2.49 318 165 Cl F Me O H H H CH2 2-bromo-3-thienyl 2.82 399 166 F F Me O H H H CH2 2-bromo-3-thienyl 2.64 382 167 F F Me O H H H CH2 4,5-dimethyl-3-thienyl 2.82 332 168 Cl F Me O H H H CH2 4,5-dimethyl-3-thienyl 3.02 348 169 Cl F Me O H H H CH2 4,5,6,7-tetrahydro-1- 3.52 374 benzo-thiophen-3-yl 170 F F Me O H H H CH2 4,5,6,7-tetrahydro-1- 3.31 358 benzo-thiophen-3-yl 171 F F Me O H H H CH2 3-methyl-1- 3.27 368 benzothiophen-2-yl 172 Cl F Me O H H H CH2 3-methyl-1- 3.46 384 benzothiophen-2-yl 173 F F Me O H Me H CH2 2-furyl 2.20 302 174 Cl F Me O H Me H CH2 2-furyl 2.37 318 175 F F Me O cyclohexyl H H CH2 pyridin-2-yl 1.48 381 176 F F Me O cyclopentyl H H CH2 pyridin-2-yl 1.29 367 177 F F Me O 2-methoxyethyl H H CH2 pyridin-2-yl 0.50 357 178 F F Me O isopropyl H H CH2 pyridin-2-yl 0.85 341 179 F F Me O methyl H H CH2 pyridin-2-yl 1.47 313 180 Cl F Me O cyclohexyl H H CH2 pyridin-2-yl 1.58 397 181 Cl F Me O cyclopentyl H H CH2 pyridin-2-yl 1.40 383 182 Cl F Me O isopropyl H H CH2 pyridin-2-yl 1.00 357 183 Cl F Me O methyl H H CH2 pyridin-2-yl 1.63 329 184 Cl F Me O 2-methoxyethyl H H CH2 pyridin-2-yl 0.63 373 185 F F Me O H CF3 H CH2 3-methylpyridin-2-yl 1.52 381 186 Cl F Me O H CF3 H CH2 3-methylpyridin-2-yl 1.70 397 187 F F Me O H H H CH2 3-chloro-5-(trifluoromethyl) 2.75 401 pyridin-2-yl 188 F F Me O cyclopropyl Me H CH2 3-chloro-5-(trifluoromethyl) 3.80 455 pyridin-2-yl 189 Cl F Me O cyclopropyl Me H CH2 3-chloro-5-(trifluoromethyl) 3.96 471 pyridin-2-yl 190 F F Me O H Me H CH2 3-chloro-5-(trifluoromethyl) 3.08 415 pyridin-2-yl 191 Cl F Me O H H H CH2 3-chloro-5-(trifluoromethyl) 2.97 pyridin-2-yl 192 F F Me O H H H CH(Et) 3-chloro-5-(trifluoromethyl) 3.52 429 pyridin-2-yl 193 Cl F Me O H H H CH(Et) 3-chloro-5-(trifluoromethyl) 3.73 445 pyridin-2-yl 194 F F Me O H Me Me C═O 3-chloro-5-(trifluoromethyl) 3.23 443 pyridin-2-yl 195 Cl F Me O H Me Me C═O 3-chloro-5-(trifluoromethyl) 3.39 459 pyridin-2-yl 196 Cl F Me O H H H CH2 6-chloropyridin-3-yl 1.90 349 197 F F Me O H H H CH2 6-chloropyridin-3-yl 1.78 333 198 F F Me O isopropyl H H CH2 pyridin-4-yl 0.78 341 199 F F Me O 2-methoxyethyl H H CH2 pyridin-4-yl 1.56 357 200 F F Me O cyclohexyl H H CH2 pyridin-4-yl 1.39 381 201 F F Me O cyclopentyl H H CH2 pyridin-4-yl 1.20 367 202 Cl F Me O 2-methoxyethyl H H CH2 pyridin-4-yl 1.69 373 203 Cl F Me O cyclohexyl H H CH2 pyridin-4-yl 1.50 397 204 Cl F Me O cyclopentyl H H CH2 pyridin-4-yl 1.32 383 205 Cl F Me O isopropyl H H CH2 pyridin-4-yl 0.98 357 206 F F Me O methyl H H CH(Me) pyridin-4-yl 1.60 327 207 Cl F Me O methyl H H CH(Me) pyridin-4-yl 1.74 343 208 F F Me O H H H CH2 2,3,5,6-tetrafluoropyridin-4-yl 2.44 371 209 Cl F Me O H H H CH2 2,3,5,6-tetrafluoropyridin-4-yl 2.60 387 210 F F Me O cyclopropyl

2-chlorophenyl 4.31 412 211 F F Me O cyclopropyl

2,4-dichlorophenyl 4.67 446 212 F F Me O H

phenyl 3.13 352 213 F F Me O H

phenyl 3.29 352 214 Cl F Me O H

phenyl 3.33 368 215 Cl F Me O H

phenyl 3.51 368 216 F F Me O cyclopropyl

2-chlorophenyl 4.49 426 217 F F Me O cyclopropyl

2,4-dichlorophenyl 5.05 460 218 F F Me O cyclopropyl

phenyl 4.18 + 4.26⁽¹⁾ 406 219 F F Me S cyclopropyl

phenyl 5.01 + 5.11⁽¹⁾ 422 220 F F Me O H

4-fluorophenyl 2.59 328 221 Cl F Me O H

4-fluorophenyl 2.75 344 222 F F Me O H

3-fluorophenyl 2.59 328 223 Cl F Me O H

3-fluorophenyl 2.75 344 224 F F Me O H

4-chlorophenyl 2.61 344 225 F F Me O H

2-(trifluoromethyl)phenyl 3.00 378 226 Cl F Me O H

2-(trifluoromethyl)phenyl 3.15 394 227 Cl F Me O H H H Si(Me)2 phenyl 3.31 358 228 F F Me O H H H Si(Me)2 phenyl 3.13 342 229 F F Me O cyclohexyl H H Si(Me)2 phenyl 4.86 424 230 F F Me O methyl H H Si(Me)2 phenyl 3.23 356 231 F F Me O cyclopropyl H H Si(Me)2 2-chlorophenyl 4.13 416 232 Cl F Me O H H H Si(Me)2 2-chlorophenyl 3.69 392 233 F F Me O H H H Si(Me)2 2-chlorophenyl 3.48 376 234 F F Me S H H H Si(Me)2 2-chlorophenyl 4.11 392 235 F F Me O cyclopropyl H H Si(Me)2 3-chlorophenyl 4.18 416 236 Cl F Me O H H H Si(Me)2 3-chlorophenyl 3.71 392 237 F F Me O H H H Si(Me)2 3-chlorophenyl 3.55 376 238 F F Me O cyclopropyl H H Si(Me)2 2,4-dichlorophenyl 4.78 450 239 Cl F Me O H H H Si(Me)2 2,4-dichlorophenyl 4.25 426 240 F F Me O H H H Si(Me)2 2,4-dichlorophenyl 4.06 410 241 F F Me S H H H Si(Me)2 2,4-dichlorophenyl 4.74 426 242 F F Me O cyclopropyl H H Si(Me)2 3,5-dichlorophenyl 4.78 450 243 Cl F Me O H H H Si(Me)2 3,5-dichlorophenyl 4.27 426 244 F F Me O H H H Si(Me)2 3,5-dichlorophenyl 4.08 410 245 F F Me O cyclopropyl H H Si(Me)2 2-naphthyl 4.36 432 246 Cl F Me O cyclopropyl H H Si(Me)2 2-naphthyl 4.51 448 247 Cl F Me O cyclopropyl H H Si(Me)2 3-thienyl 3.71 404 248 F F Me O cyclopropyl H H Si(Me)2 3-thienyl 3.55 388 249 F F Me O methyl

phenyl 3.27 + 3.46⁽¹⁾ 366 250 Cl F Me O methyl

phenyl 3.55 + 3.63⁽¹⁾ 382 Note ⁽¹⁾mixture of two isomers

The following examples illustrate in a non-limiting manner the preparation and efficacy of the compounds of formula (I) according to the invention.

PREPARATION EXAMPLE 1 Preparation of N-{1-[3-chloro-5-(trifluoromethyl)pyridin-2-yl]propan-2-yl}-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide (compound 190)

Step 1: Preparation of 5-chloro-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid (IIIa)

In a 500 ml flask, 6.0 g (31 mmol) of 5-chloro-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carbaldehyde to are added to 30 ml of toluene. A solution of 2.4 g (62 mmol) of sodium hydroxide in 6 ml of water is added to the reaction mixture, followed by 103 ml of a 30% solution of hydrogen peroxide in water, whilst keeping the temperature below 37° C. After the end of the addition, the reaction mixture is stirred at 50° C. for 7 hours. Once the reaction mixture is back to room temperature, the two phases are separated and the organic phase is extracted with 100 ml of water. The combined aqueous phases are acidified to pH 2 with aqueous hydrochloric acid. The resulting white precipitate is filtered, washed twice with 20 ml of water, and dried to yield 3.2 g of 5-chloro-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid as a white solid. ¹H NMR (400 MHz, DMSO-d₆) δ ppm: 3.78 (s, 3H); 7.12 (t, 1H, JHF=53.60 Hz) 13.19 (s, 1H); IR (KBr): 1688 cm⁻¹ (C═O); 2200-3200 cm⁻¹ broad (hydrogen bond).

Step 2: Preparation of 5-chloro-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carbonyl chloride (IIIb)

3.2 g of 5-chloro-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid and 44.3 ml of thionyl chloride are refluxed for 5 hours. After cooling down, the reaction mixture is evaporated under vacuum to yield 3.5 g of 5-chloro-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carbonyl chloride as a yellow oil. ¹H NMR (400 MHz, CHCl3-d₆) δ ppm: 3.97 (s, 3H); 7.00 (t, J=52.01 Hz, 1H); IR (TQ): 1759 and 1725 cm⁻¹ (C═O).

Step 3: Preparation of 3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carbonyl fluoride (IIIc)

To a dried solution of 4.0 g (70 mmol) of potassium fluoride in 21 ml of tetrahydrothiophene-1,1-dioxide is added a solution of 5.0 g (22 mmol) of 5-chloro-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carbonyl chloride in 15 ml of toluene at 100° C. The resulting reaction mixture is stirred at 190-200° C. for 22 hours. Distillation under vacuum yields 8 g of a solution (25% molar) of 3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carbonyl fluoride in tetrahydro-thiophene-1,1-dioxide. ¹H NMR (250 MHz, CHCl₃-d₆) δ ppm: 3.87 (s, 3H); 6.79 (t, J=53.75 Hz, 1H); ¹⁹F NMR (250 MHz, CHCl₃-d₆) δ ppm: 45.37 (s, COF); −117.5 (d, J=28.2 Hz); −131.6 (m).

Step 4: Preparation of 3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxylic acid (IIId)

To 400 ml of a 1N sodium hydroxyde aqueous solution, is added dropwise 67.5 g of a solution (10% molar) of 3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carbonyl fluoride in tetra-hydrothiophene-1,1-dioxide. The temperature is kept below 20° C. during the addition. After 2 hours of stirring at room temperature, the reaction mixture is carefully acidified to pH 2 with concentrated aqueous hydrochloric acid. The resulting white precipitate is filtered, washed with water, and dried to yield 6 g of 3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxylic acid as a white solid. ¹H NMR (400 MHz, DMSO-d₆) δ ppm: 3.90 (s, 3H); 7.22 (t, 1H, J_(HF)=53.55 Hz); 13.33 (s, 1H).

Step 5: Preparation of N-{1-[3-chloro-5-(trifluoromethyl)pyridin-2-yl]propan-2-yl}-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide

At ambient temperature, 150 mg (0.545 mmol) of 1-[3-chloro-5-(trifluoromethyl)pyridin-2-yl]propan-2-amine, 116 mg (0.60 mmol) of 3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxylic acid, 81 mg (0.60 mmol) of 1-hydroxybenzotriazole and 55 mg (0.545 mmol) of triethylamine are stirred together in 1 ml of dimethylformamide until dissolution. This solution is pourred over a 2 g-containing basic alumina Chem-Elut™ cartridge packed with 1.48 g of Si-DCC resin (1.09 mmol of DCC per g of resin) and left overnight at ambient temperature. The cartridge is then washed three times by 2 ml of acetonitrile. The solvents are removed and the crude amide is purified by column chromatography on silica gel (gradient heptane/ethyl acetate) to yield 187 mg (78% yield) of N-{1-[3-chloro-5-(trifluoromethyl)pyridin-2-yl]propan-2-yl}-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide as yellow solid (M+H=415).

PREPARATION EXAMPLE 2 Preparation of N-{1-[3-chloro-5-(trifluoromethyl)pyridin-2-yl]propan-2-yl}-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide (compound 188)

Step 1: Preparation of 3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carbonyl chloride (IIIe)

9.1 g of 3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxylic acid and 75.5 ml of thionyl chloride are refluxed for 1.5 hours. After cooling down, the reaction mixture is evaporated under vacuum to yield 10 g of 3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carbonyl chloride as a yellow oil. GC-MS; observed M/z: Molecular ion: (M⁺.)=212; fragments: (M⁺.-Cl)=177 and (M⁺.-F)=193.

Step 2: Preparation of N-{1-[3-chloro-5-(trifluoromethyl)pyridin-2-yl]propan-2-yl}-N-cyclopropyl-3-(difluoro-methyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide

At ambient temperature, a solution of 74 mg (0.35 mmol) of 3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carbonyl chloride in 2 ml of tetrahydrofurane is added dropwise to a solution of 100 mg (0.317 mmol) of N-{1-[3-chloro-5-(trifluoromethyl)pyridin-2-yl]propan-2-yl}cyclopropanamine and 0.137 ml (0.984 mmol) of triethylamine in 3 ml of tetrahydrofurane. The reaction mixture is stirred for 15 hrs at ambient temperature. The solvent is removed under vacuum and 50 ml of water are then added to the residue. The watery layer is extracted twice with ethyl acetate (2×25 ml) and the combined organic layers are successively washed by a 1 N solution of HCl, a saturated solution of potassium carbonate and brine and dried over magnesium sulfate to yield after concentration 131 mg of an oil. Column chromatography on silica gel (gradient heptane/ethyl acetate) yields 72 mg (47% yield) of N-{1-[3-chloro-5-(trifluoromethyl)pyridin-2-yl]propan-2-yl}-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide as a colorless oil (M+H=455).

PREPARATION EXAMPLE 3 Preparation of N-{1-[3-chloro-5-(trifluoromethyl)pyridin-2-yl]-2-methyl-1-oxopropan-2-yl}-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide (compound 194)

In a 13 ml Chemspeed™ vial is weighted 73 mg (0.726 mmol) of triethylamine. 3 ml of a 0.23 molar solution of 2-amino-1-[3-chloro-5-(trifluoromethyl)pyridin-2-yl]-2-methylpropan-1-one (0.594 mmole) in dichloromethane is added followed by 3 ml of a 0.26 molar solution of 3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carbonyl chloride (0.66 mmole) in dichloro-methane and stirred at ambient temperature for 15 hrs. 1 ml of water is then added and the mixture is deposited on a basic alumina cartridge (2 g) and eluted twice by 8 ml of dichloromethane. The solvents are removed to yield 57 mg (19%) of pure N-{1-[3-chloro-5-(trifluoromethyl)pyridin-2-yl]-2-methyl-1-oxopropan-2-yl}-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide as an oil (M+H=443).

PREPARATION EXAMPLE 4 Preparation of N-[1-(2,4-dichlorophenyl)-1-methoxypropan-2-yl]-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide (compound 73)

At ambient temperature, 233 mg (1.1 mmol) of 3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carbonyl chloride and 234 mg (1 mmol) of 1-(2,4-dichlorophenyl)-1-methoxypropan-2-amine are dissolved in 10 ml of dichloromethane. 121 mg (1.2 mmol) of triethylamine are added and the reaction mixture is stirred for 4 hrs at ambient temperature. The mixture is diluted by 50 ml of ethyl acetate and successively washed by a 1 N solution of HCl (twice), a saturated solution of potassium carbonate (twice) and brine and dried over magnesium sulfate. The solvents are removed and the crude amide is purified by column chromatography on silica gel (gradient heptane/ethyl acetate) to yields 400 mg (97% yield) of N-[1-(2,4-dichlorophenyl)-1-methoxypropan-2-yl]-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide as a pale yellow solid (M+H=410).

GENERAL PREPARATION EXAMPLE Thionation of Amide of Formula (I) on Chemspeed™ Apparatus

In a 13 ml Chemspeed™ vial is weighted 0.27 mmole of phosphorous pentasulfide (P₂S₅). 3 ml of a 0.18 molar solution of the amide (I) (0.54 mmole) in dioxane is added and the mixture is heated at reflux for two hours. The temperature is then cooled to 80° C. and 2.5 ml of water are added. The mixture is heated at 80° C. for one more hour. 2 ml of water are then added and the reaction mixture is extracted twice by 4 ml of dichloromethane. The organic phase is deposited on a basic alumina cartridge (2 g) and eluted twice by 8 ml of dichloromethane. The solvents are removed and the crude thioamide derivative is analyzed by LCMS and NMR. Insufficiently pure compounds are further purified by preparative LCMS.

Example A In Vivo Preventive Test on Sphaerotheca fuliginea (Cucumber)

Solvent: 49 parts by weight of N,N-dimethylformamide

Emulsifier: 1 part by weight of Alkylarylpolyglycolether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for preventive activity, young plants are sprayed with the preparation of active compound at the stated rate of application. One day after this treatment, the plants are inoculated with an aqueous spore suspension of Sphaerotheca fuliginea. Then the plants are placed in a greenhouse at approximately 23° C. and a relative atmospheric humidity of approximately 70%.

The test is evaluated 7 days after the inoculation. 0% means an efficacy which corresponds to that of the untreated control, while an efficacy of 100% means that no disease is observed.

Under these conditions, good (at least 70%) to total protection is observed at a dose of 500 ppm of active ingredient with the following compounds from table A:

TABLE A Example Efficacy 11 83 15 100 21 100 26 86 28 100 31 96 33 93 37 98 38 85 41 74 43 100 44 100 55 100 65 79 67 100 68 99 69 95 70 98 71 85 73 100 74 75 75 80 76 93 77 95 78 100 79 100 80 100 82 95 83 100 86 100 88 94 92 88 93 95 99 98 101 83 104 86 109 85 110 75 115 100 120 100 133 100 150 100 151 93 153 93 156 93 160 95 167 90 187 98 188 100 189 95 190 100 191 93 193 83 194 98 195 91 210 100 211 100 212 95 215 93 216 100 217 99 218 94 224 84 225 80 231 100 235 95 238 98 242 98 245 100

Under the same conditions, high protection (at least 90%) is observed at a dose of 500 ppm of active ingredient with compound 187 and compound 191, whereas poor protection (less than 20%) is observed with the compound of example J-1 disclosed in patent application WO-2004/074280 as in table A2.

TABLE A2 Example dose (ppm) Efficacy 187 from this invention 500 98 191 from this invention 500 93 J-1 from WO-2004/074280 500 16

Example J-1 disclosed in international patent WO-2004/074280 corresponds to N-{2-[3-chloro-5-(trifluoromethyl)pyridin-2-yl]ethyl}-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide. These results show that the compounds according to the invention have a much better biological activity than the structurally closest compounds disclosed in WO-2004/074280.

Under the same conditions, excellent protection (greater than 95%) is observed at a dose of 500 ppm of active ingredient with compound 212 (anti isomer), whereas no protection is observed with the des-fluoro analogue compound CMP1 (anti isomer) claimed in WO-2010/09466 as in table A3.

TABLE A3 Example dose (ppm) Efficacy 212 from this invention 500 95 compound CMP1 500 0

The des-fluoro analogue compound CMP1 (anti isomer) claimed in WO-2010/09466 corresponds to 3-(difluoromethyl)-1-methyl-N-[(1R,2S-1S′,2R)-2-phenylcyclohexyl]-1H-pyrazole-4-carboxamide. These results show that the compounds according to the invention have a much better biological activity than the structurally closest compounds.

Under the same conditions, excellent protection (greater than 95%) is observed at a dose of 500 ppm of active ingredient with compound 242, whereas poor protection (less than 5%) is observed with the des-fluoro analogue compound CMP2 as in table A4.

TABLE A4 Example dose (ppm) Efficacy 242 from this invention 500 98 CMP2 500 5

The des-fluoro analogue compound CMP2 (anti isomer) corresponds to N-cyclopropyl-N-{[(3,5-dichlorophenyl)(dimethyl)silyl]methyl}-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide. These results show that the compounds according to the invention have a much better biological activity than the structurally closest compounds.

Example B In Vivo Preventive Test on Alternaria solani (Tomato)

Solvent: 49 parts by weight of N,N-dimethylformamide

Emulsifier: 1 part by weight of Alkylarylpolyglycolether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for preventive activity, young plants are sprayed with the preparation of active compound at the stated rate of application. One day after this treatment, the plants are inoculated with an aqueous spore suspension of Alternaria solani. The plants remain for one day in an incubation cabinet at approximately 22° C. and a relative atmospheric humidity of 100%. Then the plants are placed in an incubation cabinet at approximately 20° C. and a relative atmospheric humidity of 96%.

The test is evaluated 7 days after the inoculation. 0% means an efficacy which corresponds to that of the untreated control while an efficacy of 100% means that no disease is observed.

Under these conditions, good (at least 70%) to total protection is observed at a dose of 500 ppm of active ingredient with the following compounds from table B:

TABLE B Example Efficacy 4 100 9 95 11 95 12 100 13 95 14 100 15 90 16 95 17 80 19 100 20 95 21 95 22 100 24 100 26 100 27 95 28 90 29 100 30 100 31 100 32 95 33 100 34 100 35 100 36 100 37 94 38 89 39 100 40 100 41 100 42 80 43 90 44 100 45 90 46 70 47 100 48 95 49 100 50 100 51 100 52 100 53 70 55 95 56 100 57 80 59 100 60 100 61 90 63 90 64 100 65 90 67 100 68 95 69 94 70 95 71 94 72 94 73 100 74 95 75 95 76 95 77 100 78 100 79 100 80 95 82 95 83 100 84 95 85 100 86 100 87 95 88 100 90 95 91 95 92 100 93 100 94 100 95 100 96 95 97 95 98 95 99 95 100 95 101 100 102 95 103 90 104 95 105 95 107 90 108 90 109 95 110 80 111 95 112 95 113 80 115 100 116 100 117 95 118 90 119 100 120 100 121 95 122 95 123 100 124 100 125 95 126 90 127 100 128 100 133 95 135 95 137 90 138 100 139 90 140 100 141 80 142 90 143 95 144 95 145 95 146 95 147 100 150 95 151 95 152 95 153 95 154 100 155 95 156 89 158 80 160 95 161 95 162 100 163 90 164 95 165 90 167 100 169 80 171 100 172 100 185 95 187 100 188 100 189 100 190 100 191 94 192 100 193 100 194 100 195 95 208 95 210 100 211 100 212 89 213 89 215 78 216 71 218 70 224 95 225 95 227 95 228 100 229 90 230 100 231 94 233 95 233 95 234 70 235 100 236 100 237 100 238 94 239 90 240 100 242 100 243 95 244 100 245 100 247 94 248 94

Under the same conditions, high protection (greater than 90%) to total protection is observed at a dose of 100 ppm of active ingredient with compound 65 and compound 66, whereas no protection is observed with the des-fluoro analogue compound CMP3 claimed in WO-2007/060166 as in table B2.

TABLE B2 Example dose (ppm) Efficacy 65 from this invention 100 90 66 from this invention 100 100 compound CMP3 100 0

The des-fluoro analogue compound CMP3 claimed in WO-2007/060166 corresponds to N-[2-(2,4-dichlorophenyl)ethyl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide. These results show that the compounds according to the invention have a much better biological activity than the structurally closest compounds.

Under the same conditions, high protection (at least 90%) is observed at a dose of 500 ppm and 100 ppm of active ingredient with compound 74 and compound 75, whereas good protection (at least 80%) to poor protection (less than 40%) is observed with the compound of example 1.02 disclosed in patent application WO-2008/148570 as in table B3.

TABLE B3 Example dose (ppm) Efficacy 74 from this invention 500 95 100 90 75 from this invention 500 95 100 95 1.02 from WO-2008/148570 500 80 100 40

Example 1.02 disclosed in international patent WO-2008/148570 corresponds to N-[2-(2,4-dichlorophenyl)-2-methoxyethyl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide. These results show that the compounds according to the invention have a much better biological activity than the structurally closest compounds disclosed in WO-2008/148570.

Under the same conditions, high protection (greater than 89%) is observed at a dose of 500 ppm and 100 ppm of active ingredient with compound 212 (anti isomer), whereas poor protection (less than 35%) to no protection is observed with the des-fluoro analogue compound CMP1 (anti isomer) claimed in WO-2010/09466 as in table B4.

TABLE B4 Example dose (ppm) Efficacy 212 from this invention 500 89 100 89 compound CMP1 500 33 100 0

The des-fluoro analogue compound CMP1 (anti isomer) claimed in WO-2010/09466 corresponds to 3-(difluoromethyl)-1-methyl-N-[(1R,2S-1S′,2R)-2-phenylcyclohexyl]-1H-pyrazole-4-carboxamide. These results show that the compounds according to the invention have a much better biological activity than the structurally closest compounds.

Example C In Vivo Preventive Test on Pyrenophora teres (Barley)

Solvent: 49 parts by weight of N,N-dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for preventive activity, young plants are sprayed with the preparation of active compound at the stated rate of application. One day after this treatment, the plants are inoculated with an aqueous spore suspension of Pyrenophora teres. The plants remain for 48 hours in an incubation cabinet at 22° C. and a relative atmospheric humidity of 100%. Then the plants are placed in a greenhouse at a temperature of approximately 20° C. and a relative atmospheric humidity of approximately 80%.

The test is evaluated 7-9 days after the inoculation. 0% means an efficacy which corresponds to that of the untreated control while an efficacy of 100% means that no disease is observed.

Under these conditions, good (at least 70%) to total protection is observed at a dose of 500 ppm of active ingredient with the following compounds from table C:

TABLE C Example Efficacy 4 95 5 80 9 95 11 100 12 100 13 100 14 100 15 100 16 100 19 100 20 100 21 100 22 100 24 95 26 100 27 95 28 100 29 100 30 100 31 100 32 100 33 100 34 100 35 100 36 95 37 100 38 100 39 100 40 94 41 100 42 100 43 100 44 100 45 100 47 100 48 100 49 94 50 100 51 100 52 100 53 94 55 100 56 100 57 70 58 100 59 100 60 100 63 94 65 100 67 100 68 100 70 100 71 100 72 100 73 100 74 95 75 100 76 100 77 80 78 100 79 100 80 100 82 100 83 100 84 100 85 100 86 100 87 94 88 100 89 100 90 100 91 100 92 100 93 100 94 100 95 100 96 100 97 100 98 94 99 100 100 94 101 70 102 100 103 100 104 100 105 94 106 90 107 95 108 100 109 100 110 100 111 100 112 100 113 90 114 80 115 100 116 100 117 100 118 94 119 100 120 100 121 100 122 94 123 95 124 95 125 100 126 100 127 100 128 94 129 90 133 100 135 95 138 95 139 90 140 95 142 78 143 89 146 100 147 100 150 78 151 100 152 100 153 80 154 100 155 100 156 100 157 80 160 100 161 100 162 95 163 95 164 100 165 95 167 100 169 100 171 100 172 100 185 94 187 100 188 100 189 95 190 100 191 100 192 100 193 100 194 100 195 100 208 100 210 100 211 100 215 100 216 95 218 100 220 100 222 100 224 100 225 100 227 100 228 100 229 70 230 100 231 100 233 100 234 100 235 100 236 100 237 100 238 100 240 100 240 95 241 100 242 100 243 100 244 95 245 100 247 100 248 100

Example D In Vivo Preventive Test on Venturia inaequalis (Apple Scab)

Solvent: 24.5 parts by weight of acetone

-   -   24.5 parts by weight of N,N-dimethylacetamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for preventive activity, young plants are sprayed with the preparation of active compound at the stated rate of application. After the spray coating has dried on, the plants are inoculated with an aqueous conidia suspension of the causal agent of apple scab (Venturia inaequalis) and then remain for 1 day in an incubation cabinet at approximately 20° C. and a relative atmospheric humidity of 100%.

The plants are then placed in a greenhouse at approximately 21° C. and a relative atmospheric humidity of approximately 90%.

The test is evaluated 10 days after the inoculation. 0% means an efficacy which corresponds to that of the untreated control, while an efficacy of 100% means that no disease is observed.

Under these conditions, high (at least 95%) to total protection is observed at a dose of 100 ppm of active ingredient with the following compounds from table D:

TABLE D Example Efficacy 44 100 55 100 65 100 66 100 67 100 70 100 70 100 73 100 74 100 75 95 76 100 77 100 80 100 82 100 83 100 86 100 108 100 109 99 115 100 120 100 133 100 160 100 187 100 188 100 190 100 210 100 211 100 224 100 224 100 231 99 235 100 238 100 242 100

Example E In Vivo Preventive Test on Septoria tritici (Wheat)

Solvent: 49 parts by weight of N,N-dimethylacetamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound or active compound combination is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for preventive activity, young plants are sprayed with the preparation of active compound or active compound combination at the stated rate of application.

After the spray coating has been dried, the plants are sprayed with a spore suspension of Septoria tritici. The plants remain for 48 hours in an incubation cabinet at approximately 20° C. and a relative atmospheric humidity of approximately 100% and afterwards for 60 hours at approximately 15° C. in a translucent incubation cabinet at a relative atmospheric humidity of approximately 100%.

The plants are placed in the greenhouse at a temperature of approximately 15° C. and a relative atmospheric humidity of approximately 80%.

The test is evaluated 21 days after the inoculation. 0% means an efficacy which corresponds to that of the untreated control, while an efficacy of 100% means that no disease is observed.

Under these conditions, good (at least 70%) to total protection is observed at a dose of 500 ppm of active ingredient with the following compounds from table E:

TABLE E Example Efficacy 11 100 13 93 26 100 41 93 44 100 55 100 65 100 66 71 73 100 74 100 75 100 76 100 77 100 82 100 83 100 86 80 88 90 99 100 106 71 107 86 108 100 109 100 120 100 133 80 151 100 160 70 187 100 188 100 189 70 190 100 194 100 210 100 211 100 230 100 231 100 233 90 235 100 238 100 242 100

Example F In Vivo Preventive Test on Blumeria graminis (Barley)

Solvent: 49 parts by weight of N,N-dimethylacetamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound or active compound combination is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for preventive activity, young plants are sprayed with the preparation of active compound or active compound combination at the stated rate of application.

After the spray coating has been dried, the plants are dusted with spores of Blumeria graminis f.sp. hordei.

The plants are placed in the greenhouse at a temperature of approximately 18° C. and a relative atmospheric humidity of approximately 80% to promote the development of mildew pustules.

The test is evaluated 7 days after the inoculation. 0% means an efficacy which corresponds to that of the untreated control, while an efficacy of 100% means that no disease is observed.

Under these conditions, good (at least 70%) to total protection is observed at a dose of 500 ppm of active ingredient with the following compounds from table F:

TABLE F Example Efficacy 11 100 13 100 26 100 41 100 44 100 55 100 65 95 66 90 70 100 73 100 74 100 75 100 76 100 77 100 83 100 86 100 88 80 99 89 107 78 109 100 115 100 120 94 133 100 151 100 160 70 187 94 188 100 189 100 190 100 194 100 210 100 211 100 230 100 231 100 235 94 238 100 242 100

Example G In Vivo Preventive Test on Fusarium nivale (Wheat)

Solvent: 49 parts by weight of N,N-dimethylacetamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound or active compound combination is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for preventive activity, young plants are sprayed with the preparation of active compound or active compound combination at the stated rate of application.

After the spray coating has been dried, the plants are slightly injured by using a sandblast and afterwards they are sprayed with a conidia suspension of Fusarium nivale (var. majus).

The plants are placed in the greenhouse under a translucent incubation cabinet at a temperature of approximately 10° C. and a relative atmospheric humidity of approximately 100%.

The test is evaluated 5 days after the inoculation. 0% means an efficacy which corresponds to that of the untreated control, while an efficacy of 100% means that no disease is observed.

Under these conditions, high (at least 80%) to total protection is observed at a dose of 500 ppm of active ingredient with the following compounds from table G:

TABLE G Example Efficacy 44 100 55 100 66 100 73 88 86 93 88 88 99 92 115 100 120 100 133 100 151 100 160 83 188 100 189 100 190 88 194 100 210 86 211 100 230 83 231 83 235 100 238 83 242 83

Example H In Vivo Curative Test on Fusarium nivale (Wheat)

Solvent: 49 parts by weight of N,N-dimethylacetamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound or active compound combination is mixed with the stated amounts of solvent and emulsifier, and the concentrate is to diluted with water to the desired concentration.

To test for curative activity, young plants are slightly injured by using a sandblast and afterwards they are sprayed with a conidia suspension of Fusarium nivale (var. majus) and placed for 24 hours in a greenhouse under a translucent incubation cabinet at a temperature of approximately 10° C. and a relative atmospheric humidity of approximately 100% and are subsequently sprayed with the preparation of active compound at the stated rate of application.

After the spray coating has been dried, the plants remain in the greenhouse under translucent incubation cloches at a temperature of approximately 10° C. and a relative atmospheric humidity of approximately 100%.

The test is evaluated 5 days after the inoculation. 0% means an efficacy which corresponds to that of the untreated control, while an efficacy of 100% means that no disease is observed.

Under these conditions, high (at least 85%) to total protection is observed at a dose of 500 ppm of active ingredient with the following compounds from table H:

TABLE H Example Efficacy 11 100 13 93 26 100 70 92 74 100 75 86 76 86 77 100 82 100 83 100 106 93 108 100 109 100

Example I In Vivo Preventive Test on Leptosphaeria nodorum (Wheat)

Solvent: 49 parts by weight of N,N-dimethylacetamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for preventive activity, young plants are sprayed with a preparation of active compound at the stated rate of application. One day after this treatment, the plants are inoculated with an aqueous spore suspension of Leptosphaeria nodorum. The plants remain for 48 hours in an incubation cabinet at 22° C. and a relative atmospheric humidity of 100%. Then the plants are placed in a greenhouse at a temperature of approximately 22° C. and a relative atmospheric humidity of approximately 90%.

The test is evaluated 7-9 days after the inoculation. 0% means an efficacy which corresponds to that of to the untreated control, while an efficacy of 100% means that no disease is observed.

Under these conditions, good (at least 70%) to total protection is observed at a dose of 500 ppm of active ingredient with the following compounds from table I:

TABLE I Example Efficacy 11 95 13 100 15 100 16 95 19 70 26 95 28 95 31 70 41 95 43 100 44 100 55 95 67 90 70 78 77 95 78 80 79 80 80 100 83 90 86 100 87 70 88 90 96 90 99 95 115 95 120 100 133 100 151 70 160 70 188 100 194 90 195 94 210 90 211 95 218 95 222 90 224 80 230 80 231 100 233 80 235 100 238 100 240 95 242 100 245 100 248 94

Example J In Vivo Preventive Test on Uromyces appendiculatus (Beans)

Solvent: 24.5 parts by weight of acetone

-   -   24.5 parts by weight of N,N-dimethylacetamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for preventive activity, young plants are sprayed with the preparation of active compound at the stated rate of application. After the spray coating has dried on, the plants are inoculated with an aqueous spore suspension of the causal agent of bean rust (Uromyces appendiculatus) and then remain for 1 day in an incubation cabinet at approximately 20° C. and a relative atmospheric humidity of 100%.

The plants are then placed in a greenhouse at approximately 21° C. and a relative atmospheric humidity of approximately 90%.

The test is evaluated 10 days after the inoculation. 0% means an efficacy which corresponds to that of the untreated control, while an efficacy of 100% means that no disease is observed.

Under these conditions, good (at least 75%) to total protection is observed at a dose of 100 ppm of active ingredient with the following compounds from table J:

TABLE J Example Efficacy 55 96 65 100 66 98 70 75 80 80 108 100 115 98 120 100 187 96 188 98 211 100 224 100 231 100 235 100 238 100 242 100

Example K In Vivo Preventive Test on Botrytis cinerea (Beans)

Solvent: 24.5 parts by weight of acetone

-   -   24.5 parts by weight of N,N-dimethylacetamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for preventive activity, young plants are sprayed with the preparation of active compound. After the spray coating has dried on, 2 small pieces of agar covered with growth of Botrytis cinerea are placed on each leaf. The inoculated plants are placed in a darkened chamber at 20° C. and a relative atmospheric humidity of 100%.

2 days after the inoculation, the size of the lesions on the leaves is evaluated. 0% means an efficacy which corresponds to that of the untreated control, while an efficacy of 100% means that no disease is observed. Under these conditions, good (at least 70%) to total protection is observed at a dose of 100 ppm of active ingredient with the following compounds from table K:

TABLE K Example Efficacy 44 99 55 100 65 100 66 99 67 89 70 100 70 100 73 99 74 93 75 95 76 72 77 97 80 100 82 98 83 98 86 100 115 93 120 94 133 100 160 100 187 100 188 98 190 96 210 100 211 100 224 100 231 99 235 99 238 100 242 100

Under the same conditions, total protection is observed at a dose of 500 ppm of active ingredient with compound 55, whereas no protection is observed with the compound of example F-3 disclosed in patent application WO-2007/060164 as in table K2.

TABLE K2 Example dose (ppm) Efficacy 55 from this invention 500 100 F-3 from WO-2007/060164 500 0

Example F-3 disclosed in international patent WO-2007/060164 corresponds to N-[1-(4-chlorophenyl)propan-2-yl]-N-cyclopropyl-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide. to These results show that the compounds according to the invention have a much better biological activity than the structurally closest compounds disclosed in WO-2007/060164.

Under the same conditions, excellent protection (greater than 95%) to total protection is observed at a dose of 100 ppm of active ingredient with compound 65 and compound 66, whereas no protection is observed with the des-fluoro analogue compound CMP3 claimed in WO-2007/060166 as in table K3.

TABLE K3 Example dose (ppm) Efficacy 65 from this invention 100 100 66 from this invention 100 99 compound CMP3 100 0

The des-fluoro analogue compound CMP3 claimed in WO-2007/060166 corresponds to N-[2-(2,4-dichlorophenyl)ethyl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide.

These results show that the compounds according to the invention have a much better biological activity than the structurally closest compounds.

Under the same conditions, total protection is observed at a dose of 500 ppm of active ingredient with compound 160, whereas poor protection (less than 30%) is observed with the compound of example 2-1 disclosed in patent application WO-2006/016708 as in table K4.

TABLE K4 Example dose (ppm) Efficacy 160 from this invention 500 100 2-1 from WO-2006/016708 500 30

Example 2-1 disclosed in international patent WO-2006/016708 corresponds to 5-chloro-1,3-dimethyl-N-[2-methyl-1-(2-naphthyl)-1-oxopropan-2-yl]-1H-pyrazole-4-carboxamide.

These results show that the compounds according to the invention have a much better biological activity than the structurally closest compounds disclosed in WO-2006/016708.

Under the same conditions, excellent protection (greater than 95%) is observed at a dose of 500 ppm of active ingredient with compound 188, whereas no protection is observed with the des-fluoro analogues compound CMP4 and compound CMP5 claimed in WO-2005/058833 as in table K5.

TABLE K5 Example dose (ppm) Efficacy 188 from this invention 500 95 compound CMP4 500 0 compound CMP5 500 0

The des-fluoro analogue compound CMP4 claimed in WO-2005/05883 corresponds to N-{1-[3-chloro-5-(trifluoromethyl)pyridin-2-yl]propan-2-yl}-N-cyclopropyl-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide and the des-fluoro analogue compound CMP5 claimed in WO-2005/05883 corresponds to N-{1-[3-chloro-5-(trifluoromethyl)pyridin-2-yl]propan-2-yl}-N-cyclopropyl-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide.

These results show that the compounds according to the invention have a much better biological activity than the structurally closest compounds.

Under the same conditions, total protection is observed at a dose of 500 ppm of active ingredient with compound 190, whereas no protection is observed with the des-fluoro analogue compound CMP6 claimed in WO-2005/058833 as in table K6.

TABLE K6 Example dose (ppm) Efficacy 190 from this invention 500 100 compound CMP6 500 0

The des-fluoro analogue compound CMP6 claimed in WO-2005/05883 corresponds to N-{1-[3-chloro-5-(trifluoromethyl)pyridin-2-yl]propan-2-yl}-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide.

These results show that the compounds according to the invention have a much better biological activity than the structurally closest compounds.

Under the same conditions, high protection (at least 90%) to total protection is observed at a dose of 500 ppm of active ingredient with compound 187 and compound 191, whereas no protection is observed with the compound of example J-1 disclosed in patent application WO-2004/074280 as in table K7.

TABLE K7 Example dose (ppm) Efficacy 187 from this invention 500 100 191 from this invention 500 91 J-1 from WO-2004/074280 500 0

Example J-1 disclosed in international patent WO-2004/074280 corresponds to N-{2-[3-chloro-5-(trifluoromethyl)pyridin-2-yl]ethyl}-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide.

These results show that the compounds according to the invention have a much better biological activity than the structurally closest compounds disclosed in WO-2004/074280.

Under the same conditions, excellent protection (greater than 95%) is observed at a dose of 500 ppm of active ingredient with compound 212 (anti isomer), whereas no protection is observed with the des-fluoro analogue compound CMP1 (anti isomer) claimed in WO-2010/094666 as in table K8.

TABLE K8 Example dose (ppm) Efficacy 212 from this invention 500 96 compound CMP1 500 0

The des-fluoro analogue compound CMP1 (anti isomer) claimed in WO-2010/09466 corresponds to 3-(difluoromethyl)-1-methyl-N-[(1R,2S-1S′,2R)-2-phenylcyclohexyl]-1H-pyrazole-4-carboxamide.

These results show that the compounds according to the invention have a much better biological activity than the structurally closest compounds.

Under the same conditions, total protection is observed at a dose of 500 ppm and 100 ppm of active ingredient with compound 224 (syn isomer), whereas good (at least 85%) to poor protection (less than 10%) is observed with the compound of example 1.001 (syn isomer) disclosed in patent application WO-2007/134799 as in table K9.

TABLE K9 Example dose (ppm) Efficacy 224 from this invention 500 100 100 100 1.001 from WO-2007/134799 500 89 100 8

Example 1.001 (syn isomer) disclosed in international patent WO-2007/134799 corresponds to N-[(1S,2S-1R′,2R)-2-(4-chlorophenyl)cyclopropyl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide.

These results show that the compounds according to the invention have a much better biological activity than the structurally closest compounds disclosed in WO-2007/134799.

Under the same conditions, total protection is observed at a dose of 500 ppm of active ingredient with compound 242, whereas poor protection (less than 10%) is observed with the des-fluoro analogue compound CMP2 as in table K10.

TABLE K10 Example dose (ppm) Efficacy 242 from this invention 500 100 CMP2 500 10

The des-fluoro analogue compound CMP2 (anti isomer) corresponds to N-cyclopropyl-N-{[(3,5-dichlorophenyl)(dimethyl)silyl]methyl}-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide.

These results show that the compounds according to the invention have a much better biological activity than the structurally closest compounds.

Example L In Vivo Preventive Test on Puccinia triticina (Wheat)

Solvent: 49 parts by weight of N,N-dimethylacetamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound or active compound combination is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for preventive activity, young plants are sprayed with the preparation of active compound or active compound combination at the stated rate of application. After the spray coating has been dried, the plants are sprayed with a spore suspension of Puccinia triticina. The plants remain for 48 hours in an incubation cabinet at approximately 20° C. and a relative atmospheric humidity of approximately 100%.

The plants are placed in the greenhouse at a temperature of approximately 20° C. and a relative atmospheric humidity of approximately 80%.

The test is evaluated 8 days after the inoculation. 0% means an efficacy which corresponds to that of the untreated control, while an efficacy of 100% means that no disease is observed.

Under these conditions, good (at least 70%) to total protection is observed at a dose of 500 ppm of active ingredient with the following compounds from table L:

TABLE L Example Efficacy 24 80 26 90 33 80 80 80 93 70 95 70 102 70 104 70 108 100 115 90 119 80 120 70 147 70 188 90 189 80 211 100 229 80 230 95 231 100 232 95 233 95 235 100 238 100 239 70 240 100 242 100 245 95

Under the same conditions, high protection (greater than 90%) is observed at a dose of 500 ppm of active ingredient with compound 188, whereas poor protection (less than 15%) is observed with the des-fluoro analogues compound CMP4 and compound CMP5 claimed in WO-2005/058833 as in table L2.

TABLE L2 Example dose (ppm) Efficacy 188 from this invention 500 90 compound CMP4 500 11 compound CMP5 500 11

The des-fluoro analogue compound CMP4 claimed in WO-2005/05883 corresponds to N-{1-[3-chloro-5-(trifluoromethyl)pyridin-2-yl]propan-2-yl}-N-cyclopropyl-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide and the des-fluoro analogue compound CMP5 claimed in WO-2005/05883 corresponds to N-{1-[3-chloro-5-(trifluoromethyl)pyridin-2-yl]propan-2-yl}-N-cyclopropyl-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide.

These results show that the compounds according to the invention have a much better biological activity than the structurally closest compounds.

Under the same conditions, excellent protection (greater than 95%) is observed at a dose of 500 ppm of active ingredient with compound 211, whereas poor protection (less than 5%) is observed with the compound of example 7 disclosed in patent application WO-2010/09466 as in table L3.

TABLE L3 Example dose (ppm) Efficacy 211 from this invention 500 98 7 from WO-2010/094666 500 5

Example 7 disclosed in international patent WO-2010/09466 corresponds to N-cyclopropyl-N-[2-(2,4-dichlorophenyl)cyclopentyl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide.

These results show that the compounds according to the invention have a much better biological activity than the structurally closest compounds disclosed in WO-2010/09466.

Example M In Vivo Protective Test on Cochliobolus miyabeanus (Rice)

Solvent: 28.5 parts by weight of acetone

Emulsifier: 1.5 part by weight of polyoxyethylene alkyl phenyl ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for protective activity, young plants are sprayed with the preparation of active compound at the stated rate of application. One day after spraying, the plants are inoculated with an aqueous spore suspension of the causal agent of rice brown spot (Cochliobolus miyabeanus). The plants are then placed in an incubator at approximately 25° C. and a relative atmospheric humidity of approximately 100% for 1 day.

The test is evaluated 4 days after the inoculation. 0% means an efficacy which corresponds to that of the control, while an efficacy of 100% means that no disease is observed.

Under these conditions, high (at least 90%) protection is observed at a dose of 250 ppm of active ingredient with the following compounds from table M:

TABLE M Example Efficacy 50 90 73 98 92 90 187 85 188 80

Under the same conditions, excellent protection (at least 95%) to good protection (at least 65%) is observed at a dose of 250 ppm, 100 ppm, 50 ppm and 10 ppm of active ingredient with compound 73, whereas excellent protection (at least 95%) to poor protection (less than 20%) is observed with the compound of example 1.14 disclosed in patent application WO-2008/148570 as in table M2.

TABLE M2 Example dose (ppm) Efficacy 73 from this invention 250 98 100 97 50 92 10 65 1.14 from WO-2008/148570 250 98 100 92 50 80 10 20

Example 1.14 disclosed in international patent WO-2008/148570 corresponds to N-[1-(2,4-dichlorophenyl)-1-methoxypropan-2-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide. These results show that the compounds according to the invention have a much better biological activity than the structurally closest compounds disclosed in WO-2008/148570.

Example N In Vivo Protective Test on Phakopsora pachyrhizi (Soybeans)

Solvent: 28.5 parts by weight of acetone

Emulsifier: 1.5 part by weight of polyoxyethylene alkyl phenyl ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for protective activity, young plants are sprayed with the preparation of active compound at the stated rate of application. One day after spraying, the plants are inoculated with an aqueous spore suspension of the causal agent of soybean rust (Phakopsora pachyrhizi). The plants are then placed in a greenhouse at approximately 20° C. and a relative atmospheric humidity of approximately 80%.

The test is evaluated 11 days after the inoculation. 0% means an efficacy which corresponds to that of the control, while an efficacy of 100% means that no disease is observed.

Under these conditions, high (at least 80%) to total protection is observed at a dose of 250 ppm of active ingredient with the following compounds from table N:

TABLE N Example Efficacy 211 80 231 80 235 100 238 85 242 99

Example O Inhibition of Fumonisin FB1 Produced by Fusarium proliferatum

Compounds were tested in microtiter plates in fumonisin-inducing liquid media (0.5 g malt extract, 1 g yeast extract, 1 g bacto peptone, 20 g Fructose,1 g KH₂PO₄, 0.3 g MgSO₄×7H₂O, 0.3 g KCl, 0.05 g ZnSO₄×7H₂O and 0.01 g CuSO₄×5H₂O per liter) containing 0.5% DMSO, inoculated with a concentrated spore suspension of Fusarium proliferatum to a final concentration of 2000 spores/ml.

Plates were covered and incubated at high humidity at 20° C. for 5 days

At start and after 5 days OD measurement at OD₆₂₀ multiple read per well (square: 3×3) was taken to calculate growth inhibition.

After 5 days samples of each culture medium were taken and diluted 1:1000 in 50% acetonitrile. The amounts of fumonisin FB1 of the samples were analysed per HPLC-MS/MS and results were used to calculate inhibition of FB1 production in comparison to a control without compound.

HPLC-MS/MS was done with the following parameters:

Ionization mode: ESI positive

Ionspray voltage: 5500V

Spraygas Temperature: 500° C.

Declustering potential: 114V

Collision energy: 51 eV

Collision gas: N₂

MRM trace: 722,3>352,3; dwell time 100 ms

HPLC column: Waters Atlantis T3 (trifunctional C18 bonding, fully endcapped)

Particle size: 3 μm

Column size: 50×2 mm

Temperature: 40° C.

Solvent A: Water+0.1% HCOOH (v/v)

Solvent B: Acetonitrile+0.1% HCOOH (v/v)

Flow: 400 μL/min

Injection volume: 5 μL

Gradient:

Time [min] A % B % 0 90 10 2 5 95 4 5 95 4.1 90 10 9 90 10

Compounds from table O showed excellent (at least 99%) to total inhibition of Fumonisin FB1 production at 50 μM. Growth inhibition of Fusarium proliferatum of these examples varied from 74 to 86% at 50 μM.

TABLE O % inhibition % inhibition Example dose (μM) FB1 production fungal growth 73 50 100 86 187 50 100 75 188 50 99 74 190 50 100 74

Example P Inhibition of Deoxynivalenol (DON) and Acetyldeoxynivalenol (Acetyl-DON) Produced by Fusarium graminearum

Compounds were tested in microtiter plates in DON-inducing liquid media (1 g (NH₄)₂HPO₄, 0.2 g MgSO₄×7H₂O, 3 g KH₂PO₄, 10 g Glycerin, 5 g NaCl and 40 g Sachharose per liter), supplemented with 10% oat extract, containing 0.5% DMSO, inoculated with a concentrated spore suspension of Fusarium graminearum to a final concentration of 2000 spores/ml.

The plate was covered and incubated at high humidity at 28° C. for 7 days.

At start and after 3 days OD measurement at OD₆₂₀ multiple read per well (square: 3×3) was taken to calculate the growth inhibition.

After 7 days 1 volume of 84/16 acetonitrile/water was added to each well and a sample of the liquid medium was taken and diluted 1:100 in 10% acetonitrile. The amounts of DON and Acetyl-DON of the samples were analysed per HPLC-MS/MS and results were used to calculate inhibition of DON/AcDON production in comparison to a control without compound.

HPLC-MS/MS was done with the following parameters:

Ionization mode: ESI negative

Ionspray voltage: −4500V

Spraygas Temperature: 500° C.

Declustering potential: −40V

Collision energy: −22 eV

Collision gas: N₂

MRM trace: 355.0>264.9; dwell time 150 ms

HPLC column: Waters Atlantis T3 (trifunctional C18 bonding, fully endcapped)

Particle size: 3 μm

Column size: 50×2 mm

Temperature: 40° C.

Solvent A: Water/2.5 mM NH₄OAc+0.05% CH₃COOH (v/v)

Solvent B: Methanol/2.5 mM NH₄OAc+0.05% CH₃COOH (v/v)

Flow: 400 μL/min

Injection volume: 11 μL

Gradient:

Time [min] A % B % 0 100 0 0.75 100 0 1.5 5 95 4 5 95 5 100 0 10 100 0

Compounds from table P showed excellent (at least 90%) to total inhibition of DON/Acetyl-DON production at 50 μM. Growth inhibition of Fusarium graminearum of these examples varied from 0% to total inhibition at 50 μM.

TABLE P % inhibition % inhibition Example dose (μM) FB1 production fungal growth 55 50 90 0 73 50 100 100 160 50 100 89 187 50 99 85 188 50 99 95 190 50 100 96

Example Q Inhibition of Aflatoxines Produced by Aspergillus parasiticus

Compounds were tested in microtiter plates (96 well black flat and transparent bottom) in Aflatoxin-inducing liquid media (20 g sucrose, yeast extract 4 g, KH₂PO₄ 1 g, and MgSO₄ 7H₂O 0.5 g per liter), supplemented with 20 mM of Cavasol (hydroxypropyl-beta-cyclodextrin) and containing 1% of DMSO. The assay is started by inoculating the medium with a concentrated spore suspension of Aspergillus parasiticus at a final concentration of 1000 spores/ml.

The plate was covered and incubated at 20° C. for 7 days.

After 7 days of culture, OD measurement at OD_(620 nm) with multiple read per well (circle: 4×4) was taken with an Infinite 1000 (Tecan) to calculate the growth inhibition. In the same time bottom fluorescence measurement at EM_(360 nm) and EX_(426 nm) with multiple read per well (square: 3×3) was taken to calculate inhibition of aflatoxin formation.

Compounds from table Q showed high (at least 86%) to total inhibition of aflatoxines production at 50 μM. Growth inhibition of Fusarium graminearum of these examples varied from 69 to 100% at 50 μM.

TABLE Q % Inhibition of % Inhibition of Aflatoxin at fungal growth at Example 50 μM 50 μM 4 100 91 11 100 100 12 100 92 13 100 100 14 100 100 15 100 83 17 100 83 19 100 100 20 86 69 22 100 100 24 100 88 26 100 99 29 100 82 30 100 98 31 100 100 32 100 99 33 100 100 34 100 84 35 100 100 36 100 94 37 94 78 39 100 100 40 99 78 41 100 100 42 100 84 43 100 90 44 100 100 47 100 100 49 100 91 50 100 100 51 100 100 52 100 83 55 100 100 56 100 93 59 100 83 60 100 96 61 100 84 65 100 100 66 100 100 67 100 100 68 100 100 69 100 86 70 100 100 73 100 100 74 100 100 75 100 100 76 100 100 77 100 100 78 100 100 79 100 98 80 100 100 82 100 100 83 100 100 84 100 100 85 100 100 86 100 98 87 100 94 88 100 86 90 100 100 91 100 100 92 100 100 93 100 100 94 100 100 95 100 100 96 100 82 97 100 100 98 100 95 100 99 85 101 100 86 102 100 100 103 100 99 104 100 98 105 100 95 106 89 69 107 98 74 108 100 100 109 100 100 111 100 96 112 100 83 115 100 100 117 100 100 118 100 81 119 95 79 120 100 100 121 100 100 123 100 100 124 100 87 125 99 78 126 100 98 127 100 100 128 100 82 129 90 70 133 100 100 135 100 96 138 100 80 146 100 83 147 93 77 151 100 94 152 100 82 154 99 80 159 98 77 160 100 100 161 100 85 162 98 80 163 98 80 164 100 95 165 99 81 166 100 97 167 100 100 168 100 97 169 91 75 170 100 95 171 100 93 172 100 85 173 100 83 174 89 76 185 100 87 187 100 100 188 100 100 189 100 90 190 100 100 191 100 100 192 100 100 193 100 91 194 100 100 195 100 81 202 99 81 207 99 37 208 99 100 210 100 100 211 100 100 212 100 99 216 100 84 218 100 99 220 100 81 222 99 81 224 100 100 225 97 83 227 87 71 228 100 93 230 100 100 231 100 100 233 88 76 235 100 100 236 99 84 237 100 100 238 100 100 240 100 84 242 100 100 243 99 84 244 100 100 245 100 100 247 100 100 248 100 100 

1. A compound of formula (I):

wherein X¹ and X² which can be the same or different, represent a halogen atom; Y represents a C₁-C₄-alkyl; T represents O or S; W represents CZ⁴Z⁵; O; S; SO; SO₂; NZ⁶; SiZ⁷Z⁸; or —C(═U)—; B represents a phenyl ring that can be substituted by up to 5 groups X which can be the same or different; a naphthyl ring that can be substituted by up to 7 groups X which can be the same or different; or a saturated, partially saturated or unsaturated, monocyclic or fused bicyclic 4-, 5-, 6-, 7-, 8-, 9-, 10-membered ring comprising from 1 up to 4 heteroaroms selected in the list consisting of N, O, S, that can be substituted by up to 6 groups X which can be the same or different; X represents a halogen atom; nitro; cyano; isonitrile; hydroxy; amino; sulfanyl; pentafluoro-λ⁶-sulfanyl; formyl; formyloxy; formylamino; substituted or non-substituted (hydroxyimino)-C₁-C₈-alkyl; substituted or non-substituted (C₁-C₈-alkoxyimino)-C₁-C₈-alkyl; substituted or non-substituted (C₂-C₈-alkenyloxyimino)-C₁-C₈-alkyl; substituted or non-substituted (C₂-C₈-alkynyloxyimino)-C₁-C₈-alkyl; substituted or non-substituted (benzyloxyimino)-C₁-C₈-alkyl; carboxy; carbamoyl; N-hydroxycarbamoyl; carbamate; substituted or non-substituted C₁-C₈-alkyl; C₁-C₈-halogenoalkyl having 1 to 5 halogen atoms; substituted or non-substituted C₂-C₈-alkenyl; C₂-C₈-halogenoalkenyl having 1 to 5 halogen atoms; substituted or non-substituted C₂-C₈-alkynyl; C₂-C₈-halogenoalkynyl having 1 to 5 halogen atoms; substituted or non-substituted C₁-C₈-alkoxy; C₁-C₈-halogenoalkoxy having 1 to 5 halogen atoms; substituted or non-substituted C₁-C₈-alkylsulfanyl; C₁-C₈-halogenoalkylsulfanyl having 1 to 5 halogen atoms; substituted or non-substituted C₁-C₈-alkylsulfinyl; C₁-C₈-halogenoalkylsulfinyl having 1 to 5 halogen atoms; substituted or non-substituted C₁-C₈-alkylsulfonyl; C₁-C₈-halogenoalkylsulfonyl having 1 to 5 halogen atoms; substituted or non-substituted C₁-C₈-alkylamino; substituted or non-substituted di-C₁-C₈-alkylamino; substituted or non-substituted C₂-C₈-alkenyloxy; C₂-C₈-halogenoalkenyloxy having 1 to 5 halogen atoms; substituted or non-substituted C₃-C₈-alkynyloxy; C₂-C₈-halogenoalkynyloxy having 1 to 5 halogen atoms; substituted or non-substituted C₃-C₇-cycloalkyl; C₃-C₇-halogenocycloalkyl having 1 to 5 halogen atoms; substituted or non-substituted (C₃-C₇-cycloalkyl)-C₁-C₈-alkyl; substituted or non-substituted (C₃-C₇-cycloalkyl)-C₂-C₈-alkenyl; substituted or non-substituted (C₃-C₇-cycloalkyl)-C₂-C₈-alkynyl; substituted or non-substituted tri(C₁-C₈-alkyl)silyl; substituted or non-substituted tri(C₁-C₈-alkyl)silyl-C₁-C₈-alkyl; substituted or non-substituted C₁-C₈-alkylcarbonyl; C₁-C₈-halogenoalkylcarbonyl having 1 to 5 halogen atoms; substituted or non-substituted C₁-C₈-alkylcarbonyloxy; C₁-C₈-halogenoalkylcarbonyloxy having 1 to 5 halogen atoms; substituted or non-substituted C₁-C₈-alkylcarbonylamino; C₁-C₈-halogenoalkyl-carbonylamino having 1 to 5 halogen atoms; substituted or non-substituted C₁-C₈-alkoxycarbonyl; C₁-C₈-halogenoalkoxycarbonyl having 1 to 5 halogen atoms; substituted or non-substituted C₁-C₈-alkyloxycarbonyloxy; C₁-C₈-halogenoalkoxycarbonyloxy having 1 to 5 halogen atoms; substituted or non-substituted C₁-C₈-alkylcarbamoyl; substituted or non-substituted di-C₁-C₈-alkylcarbamoyl; substituted or non-substituted C₁-C₈-alkylaminocarbonyloxy; substituted or non-substituted di-C₁-C₈-alkylaminocarbonyloxy; substituted or non-substituted N—(C₁-C₈-alkyl)hydroxy carbamoyl; substituted or non-substituted C₁-C₈-alkoxycarbamoyl; substituted or non-substituted N—(C₁-C₈-alkyl)-C₁-C₈-alkoxycarbamoyl; aryl that can be substituted by up to 6 groups Q which can be the same or different; C₁-C₈-arylalkyl that can be substituted by up to 6 groups Q which can be the same or different; C₂-C₈-arylalkenyl that can be substituted by up to 6 groups Q which can be the same or different; C₂-C₈-arylalkynyl that can be substituted by up to 6 groups Q which can be the same or different; aryloxy that can be substituted by up to 6 groups Q which can be the same or different; arylsulfanyl that can be substituted by up to 6 groups Q which can be the same or different; arylamino that can be substituted by up to 6 groups Q which can be the same or different; C₁-C₈-arylalkyloxy that can be substituted by up to 6 groups Q which can be the same or different; C₁-C₈-arylalkylsulfanyl that can be substituted by up to 6 groups Q which can be the same or different; or C₁-C₈-arylalkylamino that can be substituted by up to 6 groups Q which can be the same or different; or two substituents X together with the consecutive carbon atoms to which they are linked can form a 5- or 6-membered, saturated carbocycle or saturated heterocycle, which can be substituted by up to four groups Q which can be the same or different; Z¹ represents a hydrogen atom; a formyl group; a substituted or non-substituted C₁-C₈-alkyl; substituted or non substituted C₁-C₈-alkoxy; non-substituted C₃-C₇-cycloalkyl or a C₃-C₇-cycloalkyl substituted by up to 10 atoms or groups that can be the same or different and that can be selected in the list consisting of halogen atoms, cyano, C₁-C₈-alkyl, C₁-C₈-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different, C₁-C₈-alkoxy, C₁-C₈-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different, C₁-C₈-alkoxycarbonyl, C₁-C₈-halogenoalkoxycarbonyl comprising up to 9 halogen atoms that can be the same or different, C₁-C₈-alkylaminocarbonyl or di-C₁-C₈-alkylaminocarbonyl; Z², Z³, Z⁴ and Z⁵ independently represent a hydrogen atom; a halogen atom; cyano; substituted or non-substituted C₁-C₈-alkyl; C₁-C₈-halogenoalkyl having 1 to 5 halogen atoms; substituted or non-substituted C₁-C₈-alkoxy; substituted or non-substituted C₁-C₈-alkylsulfanyl; or substituted or non-substituted C₁-C₈-alkoxycarbonyl; or two substituents Z^(i) and Z^(i+1), i being an integer between 2 and 4, together with the consecutive carbon atoms to which they are linked can form a 3-, 4-, 5-, 6- or 7-membered saturated carbocycle that can be substituted by up to four groups that can be the same or different and that can be selected in the list consisting of halogen atoms, C₁-C₈-alkyl or C₁-C₂-halogenoalkyl comprising up to 5 halogen atoms that can be the same or different; Z⁶ represents a hydrogen atom; a substituted or non-substituted C₁-C₈-alkyl; a C₁-C₈-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different; a substituted or non-substituted C₂-C₈-alkenyl; a C₂-C₈-halogenoalkenyl comprising up to 9 halogen atoms that can be the same or different; a substituted or non-substituted C₃-C₈-alkynyl; a C₃-C₈-halogenoalkynyl comprising up to 9 halogen atoms that can be the same or different; a substituted or non-substituted C₃-C₇-cycloalkyl; a C₃-C₇-halogeno-cycloalkyl comprising up to 9 halogen atoms that can be the same or different; a substituted or non-substituted C₃-C₇-cycloalkyl-C₁-C₈-alkyl; formyl; a substituted or non-substituted C₁-C₈-alkylcarbonyl C₁-C₈-halogenoalkylcarbonyl comprising up to 9 halogen atoms that can be the same or different; a substituted or non-substituted C₁-C₈-alkoxycarbonyl; C₁-C₈-halogenoalkoxycarbonyl comprising up to 9 halogen atoms that can be the same or different; a substituted or non-substituted C₁-C₈-alkylsulphonyl; C₁-C₈-halogenoalkylsulphonyl comprising up to 9 halogen atoms that can be the same or different; phenylmethylene that can be substituted by up to 7 groups Q which can be the same or different; or phenylsulphonyl that can be substituted by up to 5 groups Q which can be the same or different; Z⁷ and Z⁸ independently represent a substituted or non-substituted C₁-C₈-alkyl; U represents O; S; N—OR^(a) or N—CN; R^(a) represents a hydrogen atom; a substituted or non-substituted C₁-C₄-alkyl; or a C₁-C₄-halogenoalkyl comprising up to 7 halogen atoms that can be the same or different; Q independently represents a halogen atom; cyano; nitro; substituted or non-substituted C₁-C₈-alkyl; C₁-C₈-halogenoalkyl having 1 to 9 halogen atoms that can be the same or different; substituted or non-substituted C₁-C₈-alkoxy; C₁-C₈-halogenoalkoxy having 1 to 9 halogen atoms that can be the same or different; substituted or non-substituted C₁-C₈-alkylsulfanyl; C₁-C₈-halogenoalkylsulfanyl having 1 to 9 halogen atoms that can be the same or different; substituted or non-substituted tri(C₁-C₈)alkylsilyl; substituted or non-substituted tri(C₁-C₈)alkylsilyl-C₁-C₈-alkyl; substituted or non-substituted (C₁-C₈-alkoxyimino)-C₁-C₈-alkyl; or substituted or non-substituted (benzyloxyimino)-C₁-C₈-alkyl; as well as its salts, N-oxydes, metallic complexes, metalloidic complexes and optically active isomers.
 2. A compound according to claim 1 wherein X¹ and X² independently represent a chlorine or a fluorine atom.
 3. A compound according to claim 1 wherein Y represents methyl.
 4. A compound according to claim 1 wherein T represents O.
 5. A compound according to claim 1 wherein B represents a substituted or non-substituted phenyl ring; a substituted or non-substituted naphthyl ring; a substituted or non-substituted pyridyl ring; a substituted or non-substituted thienyl ring; or a substituted or non-substituted benzothienyl ring; preferably a substituted or non-substituted phenyl ring or a substituted or non-substituted 2-pyridyl ring.
 6. A compound according to claim 1 wherein X independently represents a halogen atom; substituted or non-substituted C₁-C₈-alkyl; C₁-C₈-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different; substituted or non-substituted tri(C₁-C₈-alkyl)silyl; substituted or non-substituted C₁-C₈-alkoxy or C₁-C₈-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different; substituted or non-substituted C₁-C₈-alkylsulfanyl or C₁-C₈-halogenoalkylsulfanyl comprising up to 9 halogen atoms that can be the same or different; or wherein two consecutive substituents X together with the phenyl ring form a substituted or non-substituted cyclopentyl or cyclohexyl ring.
 7. A compound according to claim 1 wherein X independently represents fluorine, chlorine, bromine, iodine, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secbutyl, terbutyl, cyclopropyl, cyclopentyl, cyclohexyl, trimethylsilyl, methoxy, ethoxy, methylsulfanyl, ethyl sulfanyl, trifluoromethyl, trichloromethyl, difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, trifluoroethoxy, difluoromethysulfanyl, trifluoromethylsulfanyl and difluorochloro-methylsulfanyl.
 8. A compound according to claim 1 wherein Z¹ represents a hydrogen atom; a non-substituted C₃-C₇ cycloalkyl; or a C₃-C₇ cycloalkyl substituted by up to 10 groups or atoms that can be the same or different and that can be selected in the list consisting of halogen atoms, C₁-C₈-alkyl, C₁-C₈-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different, C₁-C₈-alkoxy or C₁-C₈-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different.
 9. A compound according to claim 1 wherein Z¹ represents a non-substituted C₃-C₇-cycloalkyl, preferably a cyclopropyl.
 10. A compound according to claim 1 wherein Z², Z³, Z⁴ and Z⁵ independently represent a hydrogen atom, a fluorine atom, a substituted or non-substituted C₁-C₈-alkyl or a substituted or non-substituted C₁-C₈-alkoxy.
 11. A compound according to claim 1 wherein two substituent Z^(i) and Z^(i+1), i being an integer between 2 and 4, together with the consecutive carbon atoms to which they are linked can form an optionally mono or polysubstituted 3-, 4-, 5-, 6- or 7-membered saturated carbocycle; preferably an optionally mono or polysubstituted cyclopropyl, cyclopentyl, cyclohexyl or cycloheptyl ring; more preferably a cyclopropyl, a cyclopentyl or a cyclohexyl ring.
 12. A compound according to claim 1 wherein Z³ and Z⁴ together with the consecutive carbon atoms to which they are linked can form an cyclopentyl, cyclohexyl or cycloheptyl group, that can be substituted by up to four groups that can be the same or different and that can be selected in the list consisting of fluorine, chlorine, methyl, ethyl, propyl, isopropyl, isobutyl, secbutyl, terbutyl, trifluoromethyl or difluoromethyl.
 13. A compound according to claim 1 wherein Z⁶ represents a substituted or non-substituted C₁-C₈-alkyl.
 14. A compound according to claim 1 wherein Z⁷ and Z⁸ independently represent a non-substituted C₁-C₃-alkyl, preferably a methyl.
 15. A compound according to claim 1 wherein U represents O or N—O—(C₁-C₄-alkyl).
 16. A fungicide composition comprising, as an active ingredient, an effective amount of a compound of formula (I) according to claim 1 and an agriculturally acceptable support, carrier or filler.
 17. A method for controlling phytopathogenic fungi of crops, characterized in that an agronomically effective and substantially non-phytotoxic quantity of a compound according to claim 1 is applied to the soil where plants grow or are capable of growing, to the leaves and/or the fruit of plants or to the seeds of plants.
 18. A method for controlling phytopathogenic fungi of crops, characterized in that an agronomically effective and substantially non-phytotoxic quantity of a composition according to claim 1 is applied to the soil where plants grow or are capable of growing, to the leaves and/or the fruit of plants or to the seeds of plants. 